CA2239182A1 - Olefin oligomerization process and catalyst - Google Patents
Olefin oligomerization process and catalyst Download PDFInfo
- Publication number
- CA2239182A1 CA2239182A1 CA 2239182 CA2239182A CA2239182A1 CA 2239182 A1 CA2239182 A1 CA 2239182A1 CA 2239182 CA2239182 CA 2239182 CA 2239182 A CA2239182 A CA 2239182A CA 2239182 A1 CA2239182 A1 CA 2239182A1
- Authority
- CA
- Canada
- Prior art keywords
- olefin
- catalyst
- oligomerization
- pendant
- solid
- 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.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims description 51
- 238000006384 oligomerization reaction Methods 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 34
- 230000008569 process Effects 0.000 title claims description 21
- 150000001336 alkenes Chemical class 0.000 title claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 8
- -1 organomagnesium halide Chemical class 0.000 claims abstract description 37
- 229910052796 boron Inorganic materials 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 36
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920000098 polyolefin Polymers 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000004711 α-olefin Substances 0.000 claims abstract description 15
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical group FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 40
- 229910015900 BF3 Inorganic materials 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 239000012071 phase Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000003606 oligomerizing effect Effects 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 239000013067 intermediate product Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 20
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Substances C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 150000004795 grignard reagents Chemical class 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 6
- 239000007818 Grignard reagent Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 229910000085 borane Inorganic materials 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 150000004820 halides Chemical group 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 2
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JHEPBQHNVNUAFL-AATRIKPKSA-N (e)-hex-1-en-1-ol Chemical group CCCC\C=C\O JHEPBQHNVNUAFL-AATRIKPKSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- WNEYWVBECXCQRT-UHFFFAOYSA-N 5-methylhept-1-ene Chemical compound CCC(C)CCC=C WNEYWVBECXCQRT-UHFFFAOYSA-N 0.000 description 1
- VUZUTEDRGWYHAF-UHFFFAOYSA-N 6,7-dimethyloct-1-ene Chemical compound CC(C)C(C)CCCC=C VUZUTEDRGWYHAF-UHFFFAOYSA-N 0.000 description 1
- NFTYCFXCGQYTKV-UHFFFAOYSA-N 6-methyloct-1-ene Chemical compound CCC(C)CCCC=C NFTYCFXCGQYTKV-UHFFFAOYSA-N 0.000 description 1
- BSJOLASGNWRVEH-UHFFFAOYSA-N 7,7-dimethyloct-1-ene Chemical compound CC(C)(C)CCCCC=C BSJOLASGNWRVEH-UHFFFAOYSA-N 0.000 description 1
- YKHFZRXJMPLNTJ-UHFFFAOYSA-N 7-methyloct-1-ene Chemical compound CC(C)CCCCC=C YKHFZRXJMPLNTJ-UHFFFAOYSA-N 0.000 description 1
- DMFDIYIYBVPKNT-UHFFFAOYSA-N 8-methylnon-1-ene Chemical compound CC(C)CCCCCC=C DMFDIYIYBVPKNT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101100001677 Emericella variicolor andL gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000083552 Oligomeris Species 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- POPCQNRKDVTFGA-UHFFFAOYSA-N boric acid methanol Chemical compound OC.OB(O)O POPCQNRKDVTFGA-UHFFFAOYSA-N 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- YSMZEMQBSONIMJ-UHFFFAOYSA-M magnesium;2-methanidylpropane;chloride Chemical compound [Mg+2].[Cl-].CC(C)[CH2-] YSMZEMQBSONIMJ-UHFFFAOYSA-M 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- GRYDGXUVWLGHPL-UHFFFAOYSA-M magnesium;heptane;bromide Chemical compound [Mg+2].[Br-].CCCCCC[CH2-] GRYDGXUVWLGHPL-UHFFFAOYSA-M 0.000 description 1
- HQDAZWQQKSJCTM-UHFFFAOYSA-M magnesium;octane;chloride Chemical compound [Mg+2].[Cl-].CCCCCCC[CH2-] HQDAZWQQKSJCTM-UHFFFAOYSA-M 0.000 description 1
- JFWWQYKSQVMLQU-UHFFFAOYSA-M magnesium;pentane;chloride Chemical compound [Mg+2].[Cl-].CCCC[CH2-] JFWWQYKSQVMLQU-UHFFFAOYSA-M 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
Abstract
Alpha-olefin oligomer is prepared by contacting an alpha-olefin monomer which contains from about 8 to about 20 carbon atoms with a heterogeneous catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) a boron trihalide, preferably BF3, and, optionally (iii) an organomagnesium halide.
Description
CA 02239182 1998-0~-29 W O 97/216~1 PCT~US96/19988 QLEFIN Ol IGoMERizATloN PROCFSS AND CATALYST
TECHNICAL FIELD
This invention relates generally to the preparation of alpha-olefin oligomers which are useful as synthetic lubricants and functional fluids, and 5 more particularly to a novel catalyst system and a novel catalytic process for conducting such oligomerizations.
BACKGROUND
Alpha-olefin oligomers and their use as synthetic lubricants are well-known. The oligomers are usualiy hydrogenated in order to improve their 10 stability. Hydrogenated oligomers produced from 1-alkenes, especially linear 1-alkenes, having in the range of about 8 to about 14 carbon atoms are generally deemed most suitable for use as synthetic lubricants and fluids.
Hydrogenated oligomer oils with viscosities of about 2-10 cSt at 100~C are typically used for general lubricating oil applications. These materials are, in15 general, mixtures of different percentages of dimer, trimer, tetramer, pentamer and, in the case of the higher viscosity products in this range, higher oligomers as well. For some lubricant applications, hydrogenated oligomers with still higher viscosities are desired.
While various types of alpha-olefin oligomerization catalysts have been 20 disclosed, catalysts based on boron trifluoride have proven most useful.
Patent literature on BF3-based alpha-olefin oligomerization includes U.S. Pat Nos. 2,806,072; 3,149,178; 3,382,291; 3,769,363; 3,997,621; 4,172,855;
4,218,330; 4,436,947; 4,982,026; 5,068,487; 5,191,140; 5,396,013; and 5,420,373. As indicated in these disclosures, a suitable promoter is used 25 with the BF3 to render it suitably effective for effecting the oligomerization.
Although the boron trifluoride-based catalyst systems exemplified by the above patents are effective, they are not without drawbacks or deficiencies. Chief among these are the problems of recovery and disposal of the catalyst residues. See for example U.S. Pat Nos. 4,213,001;
CA 02239l82 l998-0~-29 4,263,467; 4,308,414; 4,384,162; 4,394,2g6; 4,433,197; 4,4~4,366; and 4,981,578 which describe various ways of coping with these problems.
U.S. Pat No. 5,288,677 discloses immobilized Lewis acid catalysts and their use as catalysts for the polymerization of isobutylene, mixed butenes and copolymerization of monomers including 1-butene, ethyiene and 1-hexene. One of the catalysts used for polymerization of isobutylene is hydroxylated polybutene-1 copolymer which has been reacted with BF3 in a manner to form a sigma (cs) bond between the boron and oxygen atoms. For ease of description this copolymer is depicted in simplified form in the patent as PB-O-BF2 ("PB" referring to polybutene). Additional experiments have been conducted using PP-O-BF2 catalyst systems, such as:
PP-O-BF2/n-BuOH;
Pp-o-BF2ln-Buoi-~/cH2cl2;
PP-O-BF2/HCI;
Pp-o-BF2lHcllcH2cl2;
PP-O-BF2/HCI;
PP-O-BF2/t-BuCI; and PP-O-BF2/BF3 (gaseous BF3~
where "PP" refers to polypropylene, n-BuOH is n-butanol, CH2CI2 is methylene chloride, and t-BuCI is tertiary butyl chloride, and where the BF3 was in gaseous form. This work has shown that all of these additional systems show good reactivity in polymerizing isobutylene and styrene.
Unfortunately, all of these systems showed no reactivity to 1-octene.
SUMMARY OF THE INVENTION
This invention in one of its embodiments provides a new catalytic process for producing 1-olefin oligomers which utilizes a stable catalvst system that is very reactive at relatively high temperatures, and that is reas~ly recoverabie and reusable in further oligomerization reactions. In accordance with this embodiment, a 1-olefin having in the range of about 8 to about 20, and preferably about 8 to about 14 carbon atoms, or a mixture of two or more CA 02239182 1998-0~-29 such 1-olefins, is oligomerized by contact with a cataiyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, and (ii) a boron trihalide, most pre~erably boron trifluoride, and, optionally, (iii) an organomagnesium halide. Studies have indicated that the components (i) and (ii) form a complex under ordinary ambient temperature conditions. The oligomerization process of this invention is very easy to carry out. Oligomerization proceeds readily in short reaction periods and at convenient reaction temperatures, including room temperature.
0 This invention in another of its embodiments provides a new heterogeneous catalyst system formed form (i) a solid olefin polymer having a linear ~ackbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) an organomagnesium halide, and (iii) a boron trihalide, most preferably boron trifluoride. The available chemical evidence supports the view that the unification of these components results in the formation under ordinary ambient room temperature conditions of a novel complex which, using polypropylene having a plurality of pendant substituents as a typical example, may be depicted as follows:
(-CH-CH2-)~ (-CH-C~2-)y (CH2)n CH3 ,0~ (~
X2B 'MgX
~X~
where X is halide, x is an integer representing the number of the substituted polypropylene units in the molecule, y is an integer representing the nurnber of unsubstituted polypropylene units in the molecule, and n is an integer 30 representing the length of the carbon chain of the pendant substituents.
CA 02239182 1998-0~-29 W O 97/21651 PCT~US96/19988 This catalyst system or complex is readily prepared by combining a Grignard reagent with a solid olefin polymer having pendant omega-hydroxyalkyl groups and then combining a boron trihalide, preferably boron trifluoride, with the resultant product. Both steps are preferably conducted in a suitable anhydrous medium, such as a hydrocarbon diluent, under an inert atmosphere, using the substituted olefin polymer in finely-divided or particulate form. Both steps can be conducted at room temperature. The process for producing the catalyst system or complex forms still another embodiment of this invention.
0 One important advantage of the invented process and catalyst system is that the solid catalyst system or components can be recovered and reused repeatedly in batch-type operations and can be used for long periods of time in continuous or semi-continuous operations. Thus, in a batch-type process, the solid catalyst material can be readily separated from the product by filtration or like physical separation procedure, and used in ensuing operations. In continuous and semi-continuous operations the solid catalyst material can be used as a bed through which the olefin is passed. When using a catalyst formed from solid olefn polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups and a boron trihalide 20 without organomagnesium halide, boron trihalide is periodically introduced tothe oligomerization at intervals sufficient to maintain the catalytic activity of the catalyst system. When using catalyst formed from the olefin polymer, boron trihalide and organomagnesium halide, the solid catalyst complex is kept in an anhydrous, inert environment when not in use. In oligomerizations 25 utilizing the catalyst complex, a fresh charge of boron trihalide is completely unnecessary, at least during the extended periods of time during which the catalyst retains suitable catalytic activity. However, a fresh charge of boron trihalide can be introduced into the mixture at any suitable time, if desired.
Another feature of this invention is the fact that by utilizing appropriate 30 combinations of reaction time and temperature, oligomer product mixtures CA 02239182 1998-0~-29 WO 97/21651 PCT~US96/19988 having different proportions of dimers, trimers, tetramers, etc., can be formed.For example, by increasing the temperature products having higher proportions of dimer and trimer and smaller proportions of tetramer and higher oligomers can be formed. Similarly, by keeping the temperature 5 relatively iow and increasing the reaction period the proportion of dimer in the product mixture can be decreased.
The above and other embodiments and features of this invention will become still further apparent from the ensuing description and appended claims.
FURTHER DESCRIPTION
Olefins for Oligomerization The olefins used in making the oligomers are predominately (at least 50 mole %) C8-C20 and preferably predominately C8-C14 straight chain (i.e., linear) monoolefinically unsaturated hydrocarbons in which the olefinic unsaturation exists in the 1- or alpha-position of the straight chain. Such alpha-olefins are available as articles of commerce, and can be made by thermal cracking of paraffinic hydrocarbons or by well-known Ziegler ethylene chain growth technology. Individual olefins can be used as well as mixtures of such olefins. ~xamples of olefins that can be used are 1-octene, 1-. 20 nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, 1-eicosene and mixtures of two or more of such 1-olefins. Remotely branched 1-olefins such as 5-methyl-1-heptene, 6-methyl-1-heptene, 6-methyl-1-octene, 7-methyl-1-octene, 6,7-dimethyl-1-octene, 7,7-dimethyl-1-octene, 8-methyl-1-nonene, and iike 1-olefins can also be used especially when used together with linear 1-olefins.
The more preferred olefins are linear alpha-olefin monomers containing about 8-14 carbon atoms. The most preferred 1-olefin monomers are 1-octene, 1-decene, 1-dodecene and mixtures of any two or all three of these.
Minor amounts of up to about 50, and usually less than 25, mole % of internal and/or vinylidene olefins can be present in the olefin monomers.
CA 02239182 1998-0~-29 WO 97/21651 PCT~US96/19988 The oligomerizable olefins used in the practice of this invention can also be mixtures or combinations of olefins having an average in the range of about 8 to about 20 carbon atoms per molecuie, such as mixtures of octenes, decenes and dodecenes having an average carbon content per molecule 5 falling in this range.
Olefin Polymer with Penf~nt Ome~a-Hydroxyalkyl Groups The olefin polymer having pendant omega-hydroxyalkyl groups can be prepared in a two-stage operation. In the first stage a polymer having hydrocarbyl-borohydrocarbyl groups depending from the backbone is formed.
0 This involves either homopolymerizing or copolymerizing a hydrocarbyl borane monomer having an omega-alkenyl group (e.g., B-(5-hexen-1-yl)-9-BBN, B-(7-octen-1-yl~-9-BBN, etc.) as described for example in U.S. Pat.
Nos. 4,734,472 and 4,~51,276. The polymerization is effected using a suitable Ziegler-Natta catalyst system such as TiCI3AA/AlEt2CI (where "AA"
1~ means aluminum activated). Procedures for producing the hydrocarbylborane monomers are also described in these two patents. When forming the copolymers, the- hydrocarbyl borane having an omega-alkenyl group is copolymerized with at least one straight chain 1-olefin, preferably a straight chain 1-olefin having 3-10 (more preferably 3-6) carbon atoms or a 20 mixture of any two or more of these, most preferably propylene. The copolymers formed in this first stage may contain from 0.1 to 99.9 mole % of units derived from the hydrocarbyl borane monomer and from 99.9 to 0.1 mole % of units derived from the straight chain 1-olefin(s). Preferred copolymers have from about 1 to about 15 mole % of units derived from the 25 hydrocarbyl borane monomer and from about 99 to about 85 mole % of units derived from the straight chain 1-olefin(s).
In the second stage the hydrocarbylborane-substituted polymer formed in the first stage is reacted with an inorganic base and a peroxide, preferably sodium hydroxide and hydrogen peroxide, to form the olefin polymer having CA 02239182 1998-0~-29 W O 97/21651 PCT~US96/19988 pendant omega-hydroxyalkyl groups. Once again U.S. Pat. Nos. 4,734,472 and 4,751,276 provide a detailed description of this synthesis procedure.
Suitable olefin polymers having pendant omega-hydroxyalkyl groups comprise poly(1-alken-m-ol) polymers in which the 1-alken-~-ol units contain ~ ~ 6 to about 12 carbon atoms each, and poly(1-alkene-co-1-alken-m-ol) polymers in which the alkene units contain 3 to about 10 carbon atoms each and the 1-alken-~-ol units contain 6 to about 12 carbon atoms each. The homopolymers are typified by poly(1-hexen-6-ol) and poly(1-octen-8-ol). The copolymers include poly(1-butene-co-1-alken-m-ol) polymers, such as poly(1-butene-co-1-hexen-6-ol) and poly(1-butene-co-1-octen-8-ol); poly(1-pentene-co-1-alken-~-ol) polymers, such as poly(1-pentene-co-1-hexen-6-ol) and poly(1-pentene-co-1-hepten-7-ol); and poly(1-hexene-co-1-alken-~-ol) polymers, such as poly(1-hexene-co-1-hexen-6-ol) and poly(1-hexene-co-1-decen-10-ol). Particularly preferred olefin polymers having pendant omega-15 hydroxyalkyl groups are poly(propylene-co-1-alken-~-ol) polymers, such as poly(propylene-co-1-hexen-6-ol), poly(propylene-co-1-hepten-7-ol), poly(propylene-co-1-octen-8-ol), poly(propylene-co-1-nonen-9-ol), and poly(propylene-co-1 -decen-1 0-ol). These propylene-derived copolymers when suitably prepared have crystallinity and brush-like molecular structures with the hydroxyl groups at the ends of flexible side chains. Note in this connection, T. C. Chung, Polymer News, 1993, Volume 18, pages 38-43 and Chemtech, 1g91, Volume 21, pages 496-499. Thus they are capable of forming highly active catalytic complexes according to this invention.
Poly(propylene-co-1-hexen-6-ol) is a particularly preferred hydroxyalkyl olefin polymer for use in the practice of this invention.
Cataiyst Systems or Complexes with Organomagnesium Halide In the embodiment of this invention in which organomagnesium halide is employed in forming the catalyst system or complex, the olefin polymer having pendant omega-hydroxyalkyl groups is first reacted with an organomagnesium compound, preferably an organomagnesium halide, CA 02239182 1998-0~-29 W O 97/21651 PCT~US96/19988 commonly known as a Grignard reagent. The olefin polymer is preferably treated in a particulate or finely-divided state while suspended in an anhydrous inert medium such as paraffinic, cycloparaffinic or aromatic hydrocarbon, and under an inert atmosphere. The treatment is normally 5 conducted at ordinary room temperatures. Reaction periods of up to 8 hours or more at room temperature can be used.
Suitable hydrocarbylmagnesium halides include alkylmagnesium chlorides and bromides, such as ethylmagnesium chloride, propylmagnesiun chloride, butylmagnesium chloride, butylmagnesium bromide, 10 isobutylmagnesium chloride, pentylmagnesium chloride, heptylmagnesium bromide, octylmagnesium chloride, and the like. Cycloalkyl and aryl Grignard reagents such as phenylmagnesium chloride can also be used.
Alkylmagnesium chlorides are preferred. Grignard reagents are often regarded as containing a complex of RMgX or a complex of R2Mg and MgX2 15 in equilibrium with R2Mg and MgX2. Thus the terms organomagnesium halide and the terms of like import (e.g., hydrocarbylmagnesium halide, alkylmagnesium halide, etc.) are intended to encompass the materials commonly known as Grignard reagents, whatever their precise chemical structure or configuration may be.
2Q Opon completion of the above treatment with the Grignard reagent, the particulate or powdery product is separated and recovered from the liquid phase by filtration or other suitable solids-liquid physical separation technique such as centrifugation or decantation, and washed with an anhydrous, oxygen-free inert diluent such as hexane. Then the product is re-suspended 2~ in an anhydrous, oxygen-free inert liquid, such as a paraffinic or cycloparaffinic hydrocarbon, preferably a low boiling hydrocarbon such as hexane, and treated with boron trihaiide, preferably by bubbling boron trifluoride through the suspension at ordinary room temperature and atmospheric pressure for a suitable period of time, e.g., up to 5 or 6 hours or 30 more. The resultant product can be separated from the liquid phase, if :
CA 02239182 1998-0~-29 W O 97/21~51 PCT~US96/19988 desired, by filtration or other suitable solids-liquid physical separation technique such as centrifugation or decantation, and washed with anhydrous, oxygen-free inert diluent such as hexane. The product can be dried under vacuum at room temperature or slightly elevated temperature (e.g., up to 5 65~C) and stored under anhydrous oxygen-free conditions such as under a vacuum or under a dry inert gas such as nitrogen or argon. Alternatively the product may be kept in an anhydrous, inert liquid such as a paraffinic or cycloparaffinic hydrocarbon (e.g., hydrogenated alpha-olefin oligomer) which can be used as a medium in which the oligomerization reaction is to be 1 o conducted.
If all of the hydroxyl groups of the pendant omega-hydroxyalkyl groups of the initial olefin polymer participate in the reaction with the organomagnesium halide, and if all of the resultant -O-Mg-X groups participate in the reaction with the boron trihalide, the complex of this 15 invention as formed will typically have a magnesium:boron:haiide:oxygen atom ratio of 1:1:4:1, respectively. It will be appreciated however that not allof the hydroxyl groups need participate in either of the reactions, that not allof the groups that are reacted with the organomagnesium halide need react with the boron trihalide, and that the boron trihalide can react with some or all 20 of the hydroxyl groups that have not reacted with the organomagnesium halide. Consequently as long as the polymer contains at least one and preferably a plurality of pendant groups containing a moiety composed of one atom of magnesium, one atom of boron, four atoms of halide and one atom of oxygen -- a moiety which for convenience may be depicted as 25 -O-Mg-X-BX3- -- such polymer constitutes a composition of this invention.
Preferably at least 50%, and more preferably substantially all (i.e., at least 90%) of the initial hydroxyl groups on the polymer will have been converted into such moieties.
A few illustrative complexes of this invention are tabulated below with 30 reference to the reactants used for producing them:
P(Jly~Cf 12~f~pnt t~J~ t 3E2r~g~nt BX~
poly(propylene-co- l-hexen-6~1) BuMgC1 BF3 poly~p~opylene-co-1-hexen-6~1) AmMgC1 BC13 poly(propylene-co-l-hepten-7-ol) BuMgC1 BF3 poly(propylene-co-l-octen-8~1) iso-PrMgC1 B~3 poly(propylene-co-1-nonen-9~1) BuMgCI BC13 poly(propylene-co-l~ecen-10 ol) iso-~uMgCI BF3 poly(1-butene-co-1-hexen-6-ol) BuMgBr BF3 poly(l-~ co-l-octen-8~1) is~AmMgCI BC13 poly(1-o~,t~ co-1-penten-5~1) iso-BuMgBr BF3 Oligomerization Reaction In conducting the oligomerization process of this invention, oligomerization is effected by contacting the monomer(s) with a catalytic amount of the catalyst system. Typical catalytic amounts fall in the range of 20 about 0.~% to about 30% of the weight of the monomer to be oligomerized.
Preferably the catalyst system is used in the range of about 1% to about 15%
of the weight of the 1-olefin monomer with about 5% to about 10% being most preferred when using catalyst formed without use of organomagnesium halide component, for example formed from olef n polymer with pendant 25 omega-hydroxyalkyl groups and boron trihalide. Oligomerization temperatures are typically in the range of about 0 to about 80~C, and preferably are in the range of about 20 to about 60~C. Thus in conducting the oligomerization reactions of this invention at least a substantial portion of each individual reaction (e.g., at least for one-half of the total reaction period) 30 the oligomerization reaction is performed at one or more temperatures in the CA 02239182 1998-0~-29 W O97/21651 PCT~US96/19988 foregoing ranges. To ensure intimate contact between the liquid oligomer and heterogeneous catalyst system, the reaction mixture can be agitated during the reaction, or the liquid phase can be passed through a bed of the catalyst system. Reaction times will vary depending on the type of product 5 desired and reaction conditions used. Generally speaking reaction times will fall in the range of about 0.25 to about 3 hours. However, departures from this range are permissible whenever deemed necessary or desirable, and are within the scope of this invention.
Conventional protic catalyst promoters are not required, but can be used if desired. Among promoters that can be used are water, carboxylic acids, mineral acids, alcohols, phenols, carboxylic acid esters and anhydrides, ketones, aldehydes, hydroxy ketones, hydroxy aldehydes, alcohol alkoxylates, and mixtures of any two or more of the foregoing. If and when used, the amount of such promoter is typically from about û.001 to 15 about 0.04 moles per mole of 1-olefin monomer(s). The promoter can be mixed with the olefin feed or the promoter can be charged separately to the reactor, either entirely at the outset or portionwise as the oligomerization proceeds.
In one embodiment of the oligomerization process of this invention the 1-olefin or mixture of 1-olefins, boron trihalide, and polymer having pendant omega-hydroxyalkyl groups can be charged to the reactor in any suitable sequence. Preferably, however, the boron trihalide is introduced directly into a heterogeneous mixture of the 1-olefin and the solid polymer having pendant omega-hydroxyalkyl groups. In another embodiment, the catalyst complex or 2~ system formed from polymer having pendant omega-hydroxyalkyl groups, organomagnesium halide and boron trihalide is contacted with the 1-olefin or mixture of 1-olefins. As noted above, boron trifluoride is the preferred boron trihalide for use in forming the catalyst system.
The oligomerization reaction is typically conducted at about atmospheric pressure, but super-atmospheric pressures can be used, if -- .
~ CA 02239182 1998-0~-29 - 12 ~ Pa desired. Normally it is unnecessary to exceed pressures of about(100 psig) If it is desired to monitor the progress of the reaction, sampes of the oligomerization mixtures can be taken at suitable periods during the course of the reaction and subjected to gas chromatographic (GC) analysis. The reaction can be conducted in a single stirred reactor or in a series of reactors.
Alternatively, the reactor may contain a bed of the catalyst through which the liquid phase is continuously passed or circulated in a closed loop.
To terminate the oligomerization reaction, the reaction mixture is simply separated from the heterogeneous catalyst for further processing such 0 as distillation and/or hydrogenation. Unreacted olefin can be recovered and recycled.
As indicated above, because a heterogeneous catalyst is used in the process, the alpha-olefin oligomers can be in a series of two or more separate oligomerization reactions wherein the same solid polymer component of the catalyst is used over and over again. Thus in one of its embodiments this invention provides a process which comprises:
a) conducting a first or initial reaction of a series of separate oligomerization reactions by contacting at least one oligomerizable 1-olefin having in the range of about 8 to about 20, preferably about 8 to about 14, and most preferably about 8 to about 12 carbon atoms per molecule with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, and (ii) a boron trihalide, and, optionally, (iii) an organomagnesium halide, whereby the oligomerization results in a reaction mixture comprising a liquid alpha-olefin oligomer phase and a solids phase comprising solid olefin polymer catalyst residue;
b) separating the liquid phase and said solids phase from each other; and A.~ D~D SHE
IP~3JEP
CA 02239182 1998-0~-29 WO 97/21651 PCT~US96/19988 c) conducting another such reaction by contacting at least one oligomerizable 1-olefin having in the range of about 8 to about 20, preferably about 8 to about 14, and most preferably about 8 to about 12 carbon atoms per molecule with a catalyst system formed from (i) the separated solids phase from the preceding reaction and (ii) when the separated solids phase includes solids formed from olefin polymer having pendant omega-hydroxyalkyl groups and boron trihalide, a fresh charge of boron trihalide, and when the separated solids phase includes solids formed from olefin polymer having pendant hydroxyalkyl groups and organomagnesium halide and boron trihalide, an optional fresh charge of boron trihalide.
Thus a series of 5, 10, 15 or more successive separate oligomerization reactions can be performed in which after the end of each reaction the liquid phase and the solids phase are separated from each other, and the solids phase is reused as the catalyst or suppiemented with a fresh charge of boron trihalide (preferably boron trifluoride) to form catalyst. In either case, such catalyst is used with a fresh charge of an oligomerizable 1-olefin in conducting the next oligomerization reaction of that series of reactions. The 1-olefin can of course be varied from one run to the next.
Solvents or reaction diluents such as suitable parafFinic or naphthenic oils or paraffinic, cycloparaffinic or aromatic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, toluene, xylene, etc., can be employed if desired. Excess unreacted olefin can also serve as a diluent.
2~ Whenever deemed necessary or desirable, the oligomer can be recovered from the liquid phase in which it is formed by conventional procedures such as distillation.
In order to demonstrate the beneficial results achievable by the practice of this invention, an extended series of batch-type oligomerizations of 1-octene was carried out using a preferred catalyst system of this '. ~ 3~ r~,~
CA 02239182 1998-0~-29 invention, namely a system formed from poly(propylene-co-1-hexen-6 ol) ("PP-~H"), boron trifluoride and, in some cases, a hydrocarbon-soluble alkylmagnesium chloride. A typical procedure for producing PP-OH involves:
a) forming B-(5-hexen-1 -yl)-9-borobicyclo[3.3. 1 ]nonane ("hexenyl-9-BBN"), b) copolymerizing the hexenyl-9-BBN with propylene to form poly(propylene-co-1-hexen-6-yl-9-BBN), and c) oxidizing this boron-containing polyolefin polymer to PP-OH by use of sodium hydroxide and hydrogen peroxide.
10 Although full details for conducting such procedures, including the preparation of hexenyl-9-BBN, are published in patents and technical journals, illustrative procedures are given below. It is to be noted that the copolymerization descri~ ~ in Example 2 below is performed using a new continuous process thc ~es superior results as compared to prior batch-15 type polymerizations. Synthesis details and oligomerization procedures andresults are illustrated by the following examples.
Preparation of Hexenyl-9-BBN
A dry 2-liter flask is equipped with a magnetic stirring bar and a 20 connecting tube leading to a nitrogen source. The flask is thoroughly flushedwith nitrogen before the injection inlet is capped with a rubber serum stopple.
A slight positive pressure of nitrogen is rnaintained in the flask thereafter.
The flask is charged via syringe with 190 ~ (1.6 mole) of 1 ,5-hexadiene. To ~ nl the stirred diene solution is then added (via syringe) 800 ~t: of a 0.5 molar 9-25 BBN-THF solution. The reaction is effected with constant stirring at room temperature. After a period of three hours, excess 1,5-hexadiene and THF
solvent are stripped by distillation at reduced pressure. Pure hexenyl-9-BBN
is obtained at 130~C andL~0,~nf. 9).
1-33 kPa T.~- 5~ S r~ ~~
i CA 02239l82 l998-0~-29 Copolymerization of Propylene and Hexenyl-9-BBN in a Continuous Re~ction ~n~
In a typical operation, 15.477 9 of hexenyl-9-BBN and 200 ~ of hexane are placed in an argon filled Parr stirred pressure reactor and sealed.
5 Then 12 9 of propylene are added under N2 pressure. A slurry of 1.027 9 of TiCI3 and 4.705 9 of AlEt2CI in 80 ~ of toluene are then added under N2 pressure to catalyze the copolymerization. Additional propylene is added at 30-minute intervals with 10, 8, 6 and 5 9 of propylene added, respectively.
After the last monomer charge, the reaction is run for an additional hour before terrninating the reaction by injection of 100~ of isopropyl alcohol.
The reaction mixture is stirred for an additional 1/2 hour before venting the excess pressure and flushing the polymeric product with additional isopropyl alcohol. Some typical results for copolymerization of propylene and hexenyl-9-BBN using this continuous polymerization procedure are summarized in Table 1. The process produces copolymer with narrow compositional distribution and higher yield of borane monomer than previously reported procedures.
Table 1 20 Ru~ l~io. Mol 9G Hexcnyl-9- Mol % Hexenyl-9-BBN Rcaction Yield, %
BBN in Fecd in Copolyrncr Time, hr 3.S 3 62 2 10 4.2 5 75 3 13 5.0 3 65 25 4 13 7.f~ 5 72 ,; _ . _ : CA 02239l82 l998-0~-29 E~CAMPLE 3 Oxidation of PropylenelHexenyl-9-BBN Copolymer Propylene/hexenyl-9-BBN copolymer and 700,~ of THF are placed in a 2-liter round bottom flask equipped with septum and stirrer. To the 5 resultant non-homogenous slurry is added dropwise a solution of 19 9 of nll NaOH in 100 ~ of degassed water. The flask is then cooled to 0~C before slowiy adding 87.6 9 of degassed 30% H2O2 soiution via a double tipped needle. The reaction mixture is allowed to slowly come to room temperature before heating up to 55~C for 6 hours. The PP-OH polymer, poly(propylene-10 co-1-hexen-6-ol), is then precipitated in water, squeeze dried, and placed in a ml slurry 500 ~ of methanol. After 3 hours of vigorous stirring, approximately rr- I
75 r~ of MeOH is distilled off under N2 to remove boric acid-methanol azeotrope. The poly~~- is again precipitated in water, squeeze dried, washed with acetone, .ld dried under high vacuum at 45~C. Typical properties of the PP-OH polymer fommed in this manner and of polypropylene homopolymer made by the same polymerization method (Run No. 5) are summarized in Table 2. The PP-OH polymers of Run Nos. 6 and 7 of Table 2 were produced from the hexenyl-9-BBN polymers of Run Nos. 1 and 3 of Table 1 respectively. Molecular weights were determined by intrinsic 20 viscosity as measured in a conelplate viscometer at 1 35~C in decalin solution .
Table 2 Run No. Mol% OH in Melting Heat of Ft~sion. Intrinsic Mu, ~lmol Polymer Pt ~C J/g Viscosity none 163 62.5 2.07 230.000 6 3.5 161 54.1 1.78 183,000 7 5.0 158 44.6 1.71 174,000 AM~NO~O Sl lE{~
h~ -~JF p ._ t CA 02239l82 l998-0~-29 Without desiring to be bound by theoretical considerations, the data in Table 2 indicate that the crystallinities, shown by melting point and heat of fusion, of the PP-OH polymers are not much different from that of the polypropylene homopolymer, which is therefore attributed to a tapered structure of the PP-OH poiymer. Also, the functional groups on the side chains are concentrated at the end of the polymer chain indicating that the polypropylene units are in consecutive sequence to form crystalline phases.
Oligomeri~tion of 1-Octene with PP-OH/Boron Trifluoride Catalyst 0 A series of 15 consecutive oligomerization reactions was conducted in which the same 0.7 gram sample of poly(propylene-co-1-hexen-6-ol) was recovered by filtration after each run and reused in the next run, a procedure that was repeated ove -nd over again throughout the entire series. In each ml run the PP-OH copoly - and 20 r~ of 1-octene were charged to an air-free flask and at the start of each run BF3 was bubbled into the fresh mixture for 10 minutes while stirring the mixture. The slurry was then maintained under the selected reaction conditions for the desired reaction time. After each run the oligomer-containing reaction product was filtered to separate the PP-OH
copolymer from the liquid oligomer-containing phase. The recovered PP-OH
n~l and a new 20 ~ portion of 1-octene were charged to the flask for the next run. Table 3 summarizes the conditions used and the results obtained.
Table 4 summarizes analytical data concerning the composition of some of the oligomers formed in these runs.
v~ 13'-2 S~._C~
! ~--~/~p WO97/21651 PCTrUS96/19988 Table ~
Run No. ~ rti~n Reaction Time, Product Yield, Co,~ , %
Temp., ~C hr. g 1 7.28 50.9 2 20 1 7.31 S1.1 3 20 1 7.51 52.S
TECHNICAL FIELD
This invention relates generally to the preparation of alpha-olefin oligomers which are useful as synthetic lubricants and functional fluids, and 5 more particularly to a novel catalyst system and a novel catalytic process for conducting such oligomerizations.
BACKGROUND
Alpha-olefin oligomers and their use as synthetic lubricants are well-known. The oligomers are usualiy hydrogenated in order to improve their 10 stability. Hydrogenated oligomers produced from 1-alkenes, especially linear 1-alkenes, having in the range of about 8 to about 14 carbon atoms are generally deemed most suitable for use as synthetic lubricants and fluids.
Hydrogenated oligomer oils with viscosities of about 2-10 cSt at 100~C are typically used for general lubricating oil applications. These materials are, in15 general, mixtures of different percentages of dimer, trimer, tetramer, pentamer and, in the case of the higher viscosity products in this range, higher oligomers as well. For some lubricant applications, hydrogenated oligomers with still higher viscosities are desired.
While various types of alpha-olefin oligomerization catalysts have been 20 disclosed, catalysts based on boron trifluoride have proven most useful.
Patent literature on BF3-based alpha-olefin oligomerization includes U.S. Pat Nos. 2,806,072; 3,149,178; 3,382,291; 3,769,363; 3,997,621; 4,172,855;
4,218,330; 4,436,947; 4,982,026; 5,068,487; 5,191,140; 5,396,013; and 5,420,373. As indicated in these disclosures, a suitable promoter is used 25 with the BF3 to render it suitably effective for effecting the oligomerization.
Although the boron trifluoride-based catalyst systems exemplified by the above patents are effective, they are not without drawbacks or deficiencies. Chief among these are the problems of recovery and disposal of the catalyst residues. See for example U.S. Pat Nos. 4,213,001;
CA 02239l82 l998-0~-29 4,263,467; 4,308,414; 4,384,162; 4,394,2g6; 4,433,197; 4,4~4,366; and 4,981,578 which describe various ways of coping with these problems.
U.S. Pat No. 5,288,677 discloses immobilized Lewis acid catalysts and their use as catalysts for the polymerization of isobutylene, mixed butenes and copolymerization of monomers including 1-butene, ethyiene and 1-hexene. One of the catalysts used for polymerization of isobutylene is hydroxylated polybutene-1 copolymer which has been reacted with BF3 in a manner to form a sigma (cs) bond between the boron and oxygen atoms. For ease of description this copolymer is depicted in simplified form in the patent as PB-O-BF2 ("PB" referring to polybutene). Additional experiments have been conducted using PP-O-BF2 catalyst systems, such as:
PP-O-BF2/n-BuOH;
Pp-o-BF2ln-Buoi-~/cH2cl2;
PP-O-BF2/HCI;
Pp-o-BF2lHcllcH2cl2;
PP-O-BF2/HCI;
PP-O-BF2/t-BuCI; and PP-O-BF2/BF3 (gaseous BF3~
where "PP" refers to polypropylene, n-BuOH is n-butanol, CH2CI2 is methylene chloride, and t-BuCI is tertiary butyl chloride, and where the BF3 was in gaseous form. This work has shown that all of these additional systems show good reactivity in polymerizing isobutylene and styrene.
Unfortunately, all of these systems showed no reactivity to 1-octene.
SUMMARY OF THE INVENTION
This invention in one of its embodiments provides a new catalytic process for producing 1-olefin oligomers which utilizes a stable catalvst system that is very reactive at relatively high temperatures, and that is reas~ly recoverabie and reusable in further oligomerization reactions. In accordance with this embodiment, a 1-olefin having in the range of about 8 to about 20, and preferably about 8 to about 14 carbon atoms, or a mixture of two or more CA 02239182 1998-0~-29 such 1-olefins, is oligomerized by contact with a cataiyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, and (ii) a boron trihalide, most pre~erably boron trifluoride, and, optionally, (iii) an organomagnesium halide. Studies have indicated that the components (i) and (ii) form a complex under ordinary ambient temperature conditions. The oligomerization process of this invention is very easy to carry out. Oligomerization proceeds readily in short reaction periods and at convenient reaction temperatures, including room temperature.
0 This invention in another of its embodiments provides a new heterogeneous catalyst system formed form (i) a solid olefin polymer having a linear ~ackbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) an organomagnesium halide, and (iii) a boron trihalide, most preferably boron trifluoride. The available chemical evidence supports the view that the unification of these components results in the formation under ordinary ambient room temperature conditions of a novel complex which, using polypropylene having a plurality of pendant substituents as a typical example, may be depicted as follows:
(-CH-CH2-)~ (-CH-C~2-)y (CH2)n CH3 ,0~ (~
X2B 'MgX
~X~
where X is halide, x is an integer representing the number of the substituted polypropylene units in the molecule, y is an integer representing the nurnber of unsubstituted polypropylene units in the molecule, and n is an integer 30 representing the length of the carbon chain of the pendant substituents.
CA 02239182 1998-0~-29 W O 97/21651 PCT~US96/19988 This catalyst system or complex is readily prepared by combining a Grignard reagent with a solid olefin polymer having pendant omega-hydroxyalkyl groups and then combining a boron trihalide, preferably boron trifluoride, with the resultant product. Both steps are preferably conducted in a suitable anhydrous medium, such as a hydrocarbon diluent, under an inert atmosphere, using the substituted olefin polymer in finely-divided or particulate form. Both steps can be conducted at room temperature. The process for producing the catalyst system or complex forms still another embodiment of this invention.
0 One important advantage of the invented process and catalyst system is that the solid catalyst system or components can be recovered and reused repeatedly in batch-type operations and can be used for long periods of time in continuous or semi-continuous operations. Thus, in a batch-type process, the solid catalyst material can be readily separated from the product by filtration or like physical separation procedure, and used in ensuing operations. In continuous and semi-continuous operations the solid catalyst material can be used as a bed through which the olefin is passed. When using a catalyst formed from solid olefn polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups and a boron trihalide 20 without organomagnesium halide, boron trihalide is periodically introduced tothe oligomerization at intervals sufficient to maintain the catalytic activity of the catalyst system. When using catalyst formed from the olefin polymer, boron trihalide and organomagnesium halide, the solid catalyst complex is kept in an anhydrous, inert environment when not in use. In oligomerizations 25 utilizing the catalyst complex, a fresh charge of boron trihalide is completely unnecessary, at least during the extended periods of time during which the catalyst retains suitable catalytic activity. However, a fresh charge of boron trihalide can be introduced into the mixture at any suitable time, if desired.
Another feature of this invention is the fact that by utilizing appropriate 30 combinations of reaction time and temperature, oligomer product mixtures CA 02239182 1998-0~-29 WO 97/21651 PCT~US96/19988 having different proportions of dimers, trimers, tetramers, etc., can be formed.For example, by increasing the temperature products having higher proportions of dimer and trimer and smaller proportions of tetramer and higher oligomers can be formed. Similarly, by keeping the temperature 5 relatively iow and increasing the reaction period the proportion of dimer in the product mixture can be decreased.
The above and other embodiments and features of this invention will become still further apparent from the ensuing description and appended claims.
FURTHER DESCRIPTION
Olefins for Oligomerization The olefins used in making the oligomers are predominately (at least 50 mole %) C8-C20 and preferably predominately C8-C14 straight chain (i.e., linear) monoolefinically unsaturated hydrocarbons in which the olefinic unsaturation exists in the 1- or alpha-position of the straight chain. Such alpha-olefins are available as articles of commerce, and can be made by thermal cracking of paraffinic hydrocarbons or by well-known Ziegler ethylene chain growth technology. Individual olefins can be used as well as mixtures of such olefins. ~xamples of olefins that can be used are 1-octene, 1-. 20 nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, 1-eicosene and mixtures of two or more of such 1-olefins. Remotely branched 1-olefins such as 5-methyl-1-heptene, 6-methyl-1-heptene, 6-methyl-1-octene, 7-methyl-1-octene, 6,7-dimethyl-1-octene, 7,7-dimethyl-1-octene, 8-methyl-1-nonene, and iike 1-olefins can also be used especially when used together with linear 1-olefins.
The more preferred olefins are linear alpha-olefin monomers containing about 8-14 carbon atoms. The most preferred 1-olefin monomers are 1-octene, 1-decene, 1-dodecene and mixtures of any two or all three of these.
Minor amounts of up to about 50, and usually less than 25, mole % of internal and/or vinylidene olefins can be present in the olefin monomers.
CA 02239182 1998-0~-29 WO 97/21651 PCT~US96/19988 The oligomerizable olefins used in the practice of this invention can also be mixtures or combinations of olefins having an average in the range of about 8 to about 20 carbon atoms per molecuie, such as mixtures of octenes, decenes and dodecenes having an average carbon content per molecule 5 falling in this range.
Olefin Polymer with Penf~nt Ome~a-Hydroxyalkyl Groups The olefin polymer having pendant omega-hydroxyalkyl groups can be prepared in a two-stage operation. In the first stage a polymer having hydrocarbyl-borohydrocarbyl groups depending from the backbone is formed.
0 This involves either homopolymerizing or copolymerizing a hydrocarbyl borane monomer having an omega-alkenyl group (e.g., B-(5-hexen-1-yl)-9-BBN, B-(7-octen-1-yl~-9-BBN, etc.) as described for example in U.S. Pat.
Nos. 4,734,472 and 4,~51,276. The polymerization is effected using a suitable Ziegler-Natta catalyst system such as TiCI3AA/AlEt2CI (where "AA"
1~ means aluminum activated). Procedures for producing the hydrocarbylborane monomers are also described in these two patents. When forming the copolymers, the- hydrocarbyl borane having an omega-alkenyl group is copolymerized with at least one straight chain 1-olefin, preferably a straight chain 1-olefin having 3-10 (more preferably 3-6) carbon atoms or a 20 mixture of any two or more of these, most preferably propylene. The copolymers formed in this first stage may contain from 0.1 to 99.9 mole % of units derived from the hydrocarbyl borane monomer and from 99.9 to 0.1 mole % of units derived from the straight chain 1-olefin(s). Preferred copolymers have from about 1 to about 15 mole % of units derived from the 25 hydrocarbyl borane monomer and from about 99 to about 85 mole % of units derived from the straight chain 1-olefin(s).
In the second stage the hydrocarbylborane-substituted polymer formed in the first stage is reacted with an inorganic base and a peroxide, preferably sodium hydroxide and hydrogen peroxide, to form the olefin polymer having CA 02239182 1998-0~-29 W O 97/21651 PCT~US96/19988 pendant omega-hydroxyalkyl groups. Once again U.S. Pat. Nos. 4,734,472 and 4,751,276 provide a detailed description of this synthesis procedure.
Suitable olefin polymers having pendant omega-hydroxyalkyl groups comprise poly(1-alken-m-ol) polymers in which the 1-alken-~-ol units contain ~ ~ 6 to about 12 carbon atoms each, and poly(1-alkene-co-1-alken-m-ol) polymers in which the alkene units contain 3 to about 10 carbon atoms each and the 1-alken-~-ol units contain 6 to about 12 carbon atoms each. The homopolymers are typified by poly(1-hexen-6-ol) and poly(1-octen-8-ol). The copolymers include poly(1-butene-co-1-alken-m-ol) polymers, such as poly(1-butene-co-1-hexen-6-ol) and poly(1-butene-co-1-octen-8-ol); poly(1-pentene-co-1-alken-~-ol) polymers, such as poly(1-pentene-co-1-hexen-6-ol) and poly(1-pentene-co-1-hepten-7-ol); and poly(1-hexene-co-1-alken-~-ol) polymers, such as poly(1-hexene-co-1-hexen-6-ol) and poly(1-hexene-co-1-decen-10-ol). Particularly preferred olefin polymers having pendant omega-15 hydroxyalkyl groups are poly(propylene-co-1-alken-~-ol) polymers, such as poly(propylene-co-1-hexen-6-ol), poly(propylene-co-1-hepten-7-ol), poly(propylene-co-1-octen-8-ol), poly(propylene-co-1-nonen-9-ol), and poly(propylene-co-1 -decen-1 0-ol). These propylene-derived copolymers when suitably prepared have crystallinity and brush-like molecular structures with the hydroxyl groups at the ends of flexible side chains. Note in this connection, T. C. Chung, Polymer News, 1993, Volume 18, pages 38-43 and Chemtech, 1g91, Volume 21, pages 496-499. Thus they are capable of forming highly active catalytic complexes according to this invention.
Poly(propylene-co-1-hexen-6-ol) is a particularly preferred hydroxyalkyl olefin polymer for use in the practice of this invention.
Cataiyst Systems or Complexes with Organomagnesium Halide In the embodiment of this invention in which organomagnesium halide is employed in forming the catalyst system or complex, the olefin polymer having pendant omega-hydroxyalkyl groups is first reacted with an organomagnesium compound, preferably an organomagnesium halide, CA 02239182 1998-0~-29 W O 97/21651 PCT~US96/19988 commonly known as a Grignard reagent. The olefin polymer is preferably treated in a particulate or finely-divided state while suspended in an anhydrous inert medium such as paraffinic, cycloparaffinic or aromatic hydrocarbon, and under an inert atmosphere. The treatment is normally 5 conducted at ordinary room temperatures. Reaction periods of up to 8 hours or more at room temperature can be used.
Suitable hydrocarbylmagnesium halides include alkylmagnesium chlorides and bromides, such as ethylmagnesium chloride, propylmagnesiun chloride, butylmagnesium chloride, butylmagnesium bromide, 10 isobutylmagnesium chloride, pentylmagnesium chloride, heptylmagnesium bromide, octylmagnesium chloride, and the like. Cycloalkyl and aryl Grignard reagents such as phenylmagnesium chloride can also be used.
Alkylmagnesium chlorides are preferred. Grignard reagents are often regarded as containing a complex of RMgX or a complex of R2Mg and MgX2 15 in equilibrium with R2Mg and MgX2. Thus the terms organomagnesium halide and the terms of like import (e.g., hydrocarbylmagnesium halide, alkylmagnesium halide, etc.) are intended to encompass the materials commonly known as Grignard reagents, whatever their precise chemical structure or configuration may be.
2Q Opon completion of the above treatment with the Grignard reagent, the particulate or powdery product is separated and recovered from the liquid phase by filtration or other suitable solids-liquid physical separation technique such as centrifugation or decantation, and washed with an anhydrous, oxygen-free inert diluent such as hexane. Then the product is re-suspended 2~ in an anhydrous, oxygen-free inert liquid, such as a paraffinic or cycloparaffinic hydrocarbon, preferably a low boiling hydrocarbon such as hexane, and treated with boron trihaiide, preferably by bubbling boron trifluoride through the suspension at ordinary room temperature and atmospheric pressure for a suitable period of time, e.g., up to 5 or 6 hours or 30 more. The resultant product can be separated from the liquid phase, if :
CA 02239182 1998-0~-29 W O 97/21~51 PCT~US96/19988 desired, by filtration or other suitable solids-liquid physical separation technique such as centrifugation or decantation, and washed with anhydrous, oxygen-free inert diluent such as hexane. The product can be dried under vacuum at room temperature or slightly elevated temperature (e.g., up to 5 65~C) and stored under anhydrous oxygen-free conditions such as under a vacuum or under a dry inert gas such as nitrogen or argon. Alternatively the product may be kept in an anhydrous, inert liquid such as a paraffinic or cycloparaffinic hydrocarbon (e.g., hydrogenated alpha-olefin oligomer) which can be used as a medium in which the oligomerization reaction is to be 1 o conducted.
If all of the hydroxyl groups of the pendant omega-hydroxyalkyl groups of the initial olefin polymer participate in the reaction with the organomagnesium halide, and if all of the resultant -O-Mg-X groups participate in the reaction with the boron trihalide, the complex of this 15 invention as formed will typically have a magnesium:boron:haiide:oxygen atom ratio of 1:1:4:1, respectively. It will be appreciated however that not allof the hydroxyl groups need participate in either of the reactions, that not allof the groups that are reacted with the organomagnesium halide need react with the boron trihalide, and that the boron trihalide can react with some or all 20 of the hydroxyl groups that have not reacted with the organomagnesium halide. Consequently as long as the polymer contains at least one and preferably a plurality of pendant groups containing a moiety composed of one atom of magnesium, one atom of boron, four atoms of halide and one atom of oxygen -- a moiety which for convenience may be depicted as 25 -O-Mg-X-BX3- -- such polymer constitutes a composition of this invention.
Preferably at least 50%, and more preferably substantially all (i.e., at least 90%) of the initial hydroxyl groups on the polymer will have been converted into such moieties.
A few illustrative complexes of this invention are tabulated below with 30 reference to the reactants used for producing them:
P(Jly~Cf 12~f~pnt t~J~ t 3E2r~g~nt BX~
poly(propylene-co- l-hexen-6~1) BuMgC1 BF3 poly~p~opylene-co-1-hexen-6~1) AmMgC1 BC13 poly(propylene-co-l-hepten-7-ol) BuMgC1 BF3 poly(propylene-co-l-octen-8~1) iso-PrMgC1 B~3 poly(propylene-co-1-nonen-9~1) BuMgCI BC13 poly(propylene-co-l~ecen-10 ol) iso-~uMgCI BF3 poly(1-butene-co-1-hexen-6-ol) BuMgBr BF3 poly(l-~ co-l-octen-8~1) is~AmMgCI BC13 poly(1-o~,t~ co-1-penten-5~1) iso-BuMgBr BF3 Oligomerization Reaction In conducting the oligomerization process of this invention, oligomerization is effected by contacting the monomer(s) with a catalytic amount of the catalyst system. Typical catalytic amounts fall in the range of 20 about 0.~% to about 30% of the weight of the monomer to be oligomerized.
Preferably the catalyst system is used in the range of about 1% to about 15%
of the weight of the 1-olefin monomer with about 5% to about 10% being most preferred when using catalyst formed without use of organomagnesium halide component, for example formed from olef n polymer with pendant 25 omega-hydroxyalkyl groups and boron trihalide. Oligomerization temperatures are typically in the range of about 0 to about 80~C, and preferably are in the range of about 20 to about 60~C. Thus in conducting the oligomerization reactions of this invention at least a substantial portion of each individual reaction (e.g., at least for one-half of the total reaction period) 30 the oligomerization reaction is performed at one or more temperatures in the CA 02239182 1998-0~-29 W O97/21651 PCT~US96/19988 foregoing ranges. To ensure intimate contact between the liquid oligomer and heterogeneous catalyst system, the reaction mixture can be agitated during the reaction, or the liquid phase can be passed through a bed of the catalyst system. Reaction times will vary depending on the type of product 5 desired and reaction conditions used. Generally speaking reaction times will fall in the range of about 0.25 to about 3 hours. However, departures from this range are permissible whenever deemed necessary or desirable, and are within the scope of this invention.
Conventional protic catalyst promoters are not required, but can be used if desired. Among promoters that can be used are water, carboxylic acids, mineral acids, alcohols, phenols, carboxylic acid esters and anhydrides, ketones, aldehydes, hydroxy ketones, hydroxy aldehydes, alcohol alkoxylates, and mixtures of any two or more of the foregoing. If and when used, the amount of such promoter is typically from about û.001 to 15 about 0.04 moles per mole of 1-olefin monomer(s). The promoter can be mixed with the olefin feed or the promoter can be charged separately to the reactor, either entirely at the outset or portionwise as the oligomerization proceeds.
In one embodiment of the oligomerization process of this invention the 1-olefin or mixture of 1-olefins, boron trihalide, and polymer having pendant omega-hydroxyalkyl groups can be charged to the reactor in any suitable sequence. Preferably, however, the boron trihalide is introduced directly into a heterogeneous mixture of the 1-olefin and the solid polymer having pendant omega-hydroxyalkyl groups. In another embodiment, the catalyst complex or 2~ system formed from polymer having pendant omega-hydroxyalkyl groups, organomagnesium halide and boron trihalide is contacted with the 1-olefin or mixture of 1-olefins. As noted above, boron trifluoride is the preferred boron trihalide for use in forming the catalyst system.
The oligomerization reaction is typically conducted at about atmospheric pressure, but super-atmospheric pressures can be used, if -- .
~ CA 02239182 1998-0~-29 - 12 ~ Pa desired. Normally it is unnecessary to exceed pressures of about(100 psig) If it is desired to monitor the progress of the reaction, sampes of the oligomerization mixtures can be taken at suitable periods during the course of the reaction and subjected to gas chromatographic (GC) analysis. The reaction can be conducted in a single stirred reactor or in a series of reactors.
Alternatively, the reactor may contain a bed of the catalyst through which the liquid phase is continuously passed or circulated in a closed loop.
To terminate the oligomerization reaction, the reaction mixture is simply separated from the heterogeneous catalyst for further processing such 0 as distillation and/or hydrogenation. Unreacted olefin can be recovered and recycled.
As indicated above, because a heterogeneous catalyst is used in the process, the alpha-olefin oligomers can be in a series of two or more separate oligomerization reactions wherein the same solid polymer component of the catalyst is used over and over again. Thus in one of its embodiments this invention provides a process which comprises:
a) conducting a first or initial reaction of a series of separate oligomerization reactions by contacting at least one oligomerizable 1-olefin having in the range of about 8 to about 20, preferably about 8 to about 14, and most preferably about 8 to about 12 carbon atoms per molecule with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, and (ii) a boron trihalide, and, optionally, (iii) an organomagnesium halide, whereby the oligomerization results in a reaction mixture comprising a liquid alpha-olefin oligomer phase and a solids phase comprising solid olefin polymer catalyst residue;
b) separating the liquid phase and said solids phase from each other; and A.~ D~D SHE
IP~3JEP
CA 02239182 1998-0~-29 WO 97/21651 PCT~US96/19988 c) conducting another such reaction by contacting at least one oligomerizable 1-olefin having in the range of about 8 to about 20, preferably about 8 to about 14, and most preferably about 8 to about 12 carbon atoms per molecule with a catalyst system formed from (i) the separated solids phase from the preceding reaction and (ii) when the separated solids phase includes solids formed from olefin polymer having pendant omega-hydroxyalkyl groups and boron trihalide, a fresh charge of boron trihalide, and when the separated solids phase includes solids formed from olefin polymer having pendant hydroxyalkyl groups and organomagnesium halide and boron trihalide, an optional fresh charge of boron trihalide.
Thus a series of 5, 10, 15 or more successive separate oligomerization reactions can be performed in which after the end of each reaction the liquid phase and the solids phase are separated from each other, and the solids phase is reused as the catalyst or suppiemented with a fresh charge of boron trihalide (preferably boron trifluoride) to form catalyst. In either case, such catalyst is used with a fresh charge of an oligomerizable 1-olefin in conducting the next oligomerization reaction of that series of reactions. The 1-olefin can of course be varied from one run to the next.
Solvents or reaction diluents such as suitable parafFinic or naphthenic oils or paraffinic, cycloparaffinic or aromatic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, toluene, xylene, etc., can be employed if desired. Excess unreacted olefin can also serve as a diluent.
2~ Whenever deemed necessary or desirable, the oligomer can be recovered from the liquid phase in which it is formed by conventional procedures such as distillation.
In order to demonstrate the beneficial results achievable by the practice of this invention, an extended series of batch-type oligomerizations of 1-octene was carried out using a preferred catalyst system of this '. ~ 3~ r~,~
CA 02239182 1998-0~-29 invention, namely a system formed from poly(propylene-co-1-hexen-6 ol) ("PP-~H"), boron trifluoride and, in some cases, a hydrocarbon-soluble alkylmagnesium chloride. A typical procedure for producing PP-OH involves:
a) forming B-(5-hexen-1 -yl)-9-borobicyclo[3.3. 1 ]nonane ("hexenyl-9-BBN"), b) copolymerizing the hexenyl-9-BBN with propylene to form poly(propylene-co-1-hexen-6-yl-9-BBN), and c) oxidizing this boron-containing polyolefin polymer to PP-OH by use of sodium hydroxide and hydrogen peroxide.
10 Although full details for conducting such procedures, including the preparation of hexenyl-9-BBN, are published in patents and technical journals, illustrative procedures are given below. It is to be noted that the copolymerization descri~ ~ in Example 2 below is performed using a new continuous process thc ~es superior results as compared to prior batch-15 type polymerizations. Synthesis details and oligomerization procedures andresults are illustrated by the following examples.
Preparation of Hexenyl-9-BBN
A dry 2-liter flask is equipped with a magnetic stirring bar and a 20 connecting tube leading to a nitrogen source. The flask is thoroughly flushedwith nitrogen before the injection inlet is capped with a rubber serum stopple.
A slight positive pressure of nitrogen is rnaintained in the flask thereafter.
The flask is charged via syringe with 190 ~ (1.6 mole) of 1 ,5-hexadiene. To ~ nl the stirred diene solution is then added (via syringe) 800 ~t: of a 0.5 molar 9-25 BBN-THF solution. The reaction is effected with constant stirring at room temperature. After a period of three hours, excess 1,5-hexadiene and THF
solvent are stripped by distillation at reduced pressure. Pure hexenyl-9-BBN
is obtained at 130~C andL~0,~nf. 9).
1-33 kPa T.~- 5~ S r~ ~~
i CA 02239l82 l998-0~-29 Copolymerization of Propylene and Hexenyl-9-BBN in a Continuous Re~ction ~n~
In a typical operation, 15.477 9 of hexenyl-9-BBN and 200 ~ of hexane are placed in an argon filled Parr stirred pressure reactor and sealed.
5 Then 12 9 of propylene are added under N2 pressure. A slurry of 1.027 9 of TiCI3 and 4.705 9 of AlEt2CI in 80 ~ of toluene are then added under N2 pressure to catalyze the copolymerization. Additional propylene is added at 30-minute intervals with 10, 8, 6 and 5 9 of propylene added, respectively.
After the last monomer charge, the reaction is run for an additional hour before terrninating the reaction by injection of 100~ of isopropyl alcohol.
The reaction mixture is stirred for an additional 1/2 hour before venting the excess pressure and flushing the polymeric product with additional isopropyl alcohol. Some typical results for copolymerization of propylene and hexenyl-9-BBN using this continuous polymerization procedure are summarized in Table 1. The process produces copolymer with narrow compositional distribution and higher yield of borane monomer than previously reported procedures.
Table 1 20 Ru~ l~io. Mol 9G Hexcnyl-9- Mol % Hexenyl-9-BBN Rcaction Yield, %
BBN in Fecd in Copolyrncr Time, hr 3.S 3 62 2 10 4.2 5 75 3 13 5.0 3 65 25 4 13 7.f~ 5 72 ,; _ . _ : CA 02239l82 l998-0~-29 E~CAMPLE 3 Oxidation of PropylenelHexenyl-9-BBN Copolymer Propylene/hexenyl-9-BBN copolymer and 700,~ of THF are placed in a 2-liter round bottom flask equipped with septum and stirrer. To the 5 resultant non-homogenous slurry is added dropwise a solution of 19 9 of nll NaOH in 100 ~ of degassed water. The flask is then cooled to 0~C before slowiy adding 87.6 9 of degassed 30% H2O2 soiution via a double tipped needle. The reaction mixture is allowed to slowly come to room temperature before heating up to 55~C for 6 hours. The PP-OH polymer, poly(propylene-10 co-1-hexen-6-ol), is then precipitated in water, squeeze dried, and placed in a ml slurry 500 ~ of methanol. After 3 hours of vigorous stirring, approximately rr- I
75 r~ of MeOH is distilled off under N2 to remove boric acid-methanol azeotrope. The poly~~- is again precipitated in water, squeeze dried, washed with acetone, .ld dried under high vacuum at 45~C. Typical properties of the PP-OH polymer fommed in this manner and of polypropylene homopolymer made by the same polymerization method (Run No. 5) are summarized in Table 2. The PP-OH polymers of Run Nos. 6 and 7 of Table 2 were produced from the hexenyl-9-BBN polymers of Run Nos. 1 and 3 of Table 1 respectively. Molecular weights were determined by intrinsic 20 viscosity as measured in a conelplate viscometer at 1 35~C in decalin solution .
Table 2 Run No. Mol% OH in Melting Heat of Ft~sion. Intrinsic Mu, ~lmol Polymer Pt ~C J/g Viscosity none 163 62.5 2.07 230.000 6 3.5 161 54.1 1.78 183,000 7 5.0 158 44.6 1.71 174,000 AM~NO~O Sl lE{~
h~ -~JF p ._ t CA 02239l82 l998-0~-29 Without desiring to be bound by theoretical considerations, the data in Table 2 indicate that the crystallinities, shown by melting point and heat of fusion, of the PP-OH polymers are not much different from that of the polypropylene homopolymer, which is therefore attributed to a tapered structure of the PP-OH poiymer. Also, the functional groups on the side chains are concentrated at the end of the polymer chain indicating that the polypropylene units are in consecutive sequence to form crystalline phases.
Oligomeri~tion of 1-Octene with PP-OH/Boron Trifluoride Catalyst 0 A series of 15 consecutive oligomerization reactions was conducted in which the same 0.7 gram sample of poly(propylene-co-1-hexen-6-ol) was recovered by filtration after each run and reused in the next run, a procedure that was repeated ove -nd over again throughout the entire series. In each ml run the PP-OH copoly - and 20 r~ of 1-octene were charged to an air-free flask and at the start of each run BF3 was bubbled into the fresh mixture for 10 minutes while stirring the mixture. The slurry was then maintained under the selected reaction conditions for the desired reaction time. After each run the oligomer-containing reaction product was filtered to separate the PP-OH
copolymer from the liquid oligomer-containing phase. The recovered PP-OH
n~l and a new 20 ~ portion of 1-octene were charged to the flask for the next run. Table 3 summarizes the conditions used and the results obtained.
Table 4 summarizes analytical data concerning the composition of some of the oligomers formed in these runs.
v~ 13'-2 S~._C~
! ~--~/~p WO97/21651 PCTrUS96/19988 Table ~
Run No. ~ rti~n Reaction Time, Product Yield, Co,~ , %
Temp., ~C hr. g 1 7.28 50.9 2 20 1 7.31 S1.1 3 20 1 7.51 52.S
4 20 ~ 7.40 51.7 1 7.14 49.9 7 20 1 7.32 51.1 8 20 1 7.28 S0.9 9 20 1 7.38 51.6 1.S 9.60 67.1 11 20 1 7.24 50.6 12 40 1 9.98 69.8 13 60 1 13.3S 93.3 14 60 0.5 6.91 48.3 lS 20 1.5 10.40 72.7 ZO
Table 4 Run No. I~imer, % Truner, % Te~amcr, % reu~-l.,., %
7.8 56.9 18.9 16.4 4 8.1 58.6 17.8 14.5 1'' 14.5 73.7 9.S 2.3 13 33.4 59.8 6.8 trace 14 35.4 64.0 0.6 --lS 5.8 66.0 17.1 11.1 _ CA 0 2 2 3 9 1 8 2 1 9 9 8 0 ~ 2 9 EXAMP~E 5 Pre~aration of Catalyst Complex from PP-OH. Gri~nard Rea~ent and Boron Trifluoride Poly(propylene-co-1-hexen-6-ol (PP-OH polymer)) containing 3 mole 5 % of hexenol groups, prepared as in Example 3, is ground to a fine powder and vacuum dried for two hours. In a dry nitrogen atmosphere, the dried PP
OH polymer (6 grams) is suspended in 40,~ of anhydrous, oxygen-free hexane, and then 50 mmol of butylmagnesium chloride is introduced into the slurry. The mixture is kept at room temperature for five hours. The resultant 10 complex (PP-OH-Mg-CI) is in the form of powdery solids, and is separated from the liquid phase by filtration through a glass frit and washed three times with anhydrous, oxygen-free hexane. The PP-O-Mg-CI powder is then resuspended in 40 ~ of dry, oxygen-free hexane, and while continuously stirring the mixture, boron trifluoride is introduced at atmospheric pressure ~5 c~r ~ th~ee-h~ur pe~i~. T. he !;~it~ are again seqaratç~ by filtration using a glass frit and washed three times with anhydrous, oxygen-free hexane. The washed powdery product, PP-O-Mg-CI-BF3 complex, is dried under vacuum for several hours. A sample of a complex formed from the PP-OH, Grignard reagent and BF3 in this manner was subjected to structure characterization~0 and was found to have an Mg:B:F atom ratio of 1:1:3.
Oligomeri7~tion of 1-Octene with C~talyst Complex from PP-OH. Grignard Reagent ~nd Roron Trifluoride ~ C~lyst A series of 12 consecutive oligomerization reactions was conducted in 25 which the same 1 gram sample of PP-O-Mg-CI-BF3 complex produced as in Example 5 was recovered by filtration after each run in a dry box and reused in the next run, a procedure that was repeated over and over again rn I
throughout the entire series. In each run powdery soJid complex and 10 r,~
of fresh 1-octene were charged to an air-free 50 ~ flask and the mixture 30 was heated up to 60~C for the desired reaction time. After each run the IENDED SHE~;, IP~AIEP
W O 97/21651 PCT~US96/19988 oligomer-containing reaction product was filtered to separate the catalyst complex from the liquid oligomer-containing phase for use in the next run.
The separated liquid phase was distilled under vacuum to remove unreacted 1-octene monomer. Elemental analysis of the recovered catalyst after the 5 last run of the series showed that almost no change in BF3 concentration in the catalyst occurred after 12 reaction cycles. Table 5 summarizes the conditions used and the results obtained in these 12 runs. Table 6 summarizes analytical data concerning the composition of some of the oligomers formed in these runs.
Table 5 Run No. Re~ion R~eno~ Ti~, Product Yield, Col~vc.~on, Temp., ~C hr. g 1 60 2 1.62 22.7 2 60 2 1.84 Z5.7 3 60 2 1.74 24.3 4 60 2 1.78 24.9 3 2.45 34.2 6 60 4 3.04 42.5 7 60 2 1.72 24.1 8 60 2 1.85 25.8 9 60 2 1.74 24.3 2 1.80 25.1 11 60 3 2.29 32.0 12 60 4 3.10 43.3 W O97/21651 PCT~US96/19988 Table 6 ~un No. D~ner, % Tr~ner, % Teo~mer, % P~u~uue~, %
3 55.5 42.5 2.0 none 8 58.3 40.7 1.0 none 0 The entire disciosure of each and every U.S. patent and each and every technical publication referred to in any portion of this specification is incorporated herein by reference for all purposes.
This invention is susceptible to considerable variation in its practice.
Therefore the foregoing description is not intended to limit, and shouid not be construed as limiting, the invention to the particular exemplifications presented hereinabove. Rather, what is intended to be covered is as set forth in the ensuing claims and the equivalents thereof permitted as a matter of law.
Table 4 Run No. I~imer, % Truner, % Te~amcr, % reu~-l.,., %
7.8 56.9 18.9 16.4 4 8.1 58.6 17.8 14.5 1'' 14.5 73.7 9.S 2.3 13 33.4 59.8 6.8 trace 14 35.4 64.0 0.6 --lS 5.8 66.0 17.1 11.1 _ CA 0 2 2 3 9 1 8 2 1 9 9 8 0 ~ 2 9 EXAMP~E 5 Pre~aration of Catalyst Complex from PP-OH. Gri~nard Rea~ent and Boron Trifluoride Poly(propylene-co-1-hexen-6-ol (PP-OH polymer)) containing 3 mole 5 % of hexenol groups, prepared as in Example 3, is ground to a fine powder and vacuum dried for two hours. In a dry nitrogen atmosphere, the dried PP
OH polymer (6 grams) is suspended in 40,~ of anhydrous, oxygen-free hexane, and then 50 mmol of butylmagnesium chloride is introduced into the slurry. The mixture is kept at room temperature for five hours. The resultant 10 complex (PP-OH-Mg-CI) is in the form of powdery solids, and is separated from the liquid phase by filtration through a glass frit and washed three times with anhydrous, oxygen-free hexane. The PP-O-Mg-CI powder is then resuspended in 40 ~ of dry, oxygen-free hexane, and while continuously stirring the mixture, boron trifluoride is introduced at atmospheric pressure ~5 c~r ~ th~ee-h~ur pe~i~. T. he !;~it~ are again seqaratç~ by filtration using a glass frit and washed three times with anhydrous, oxygen-free hexane. The washed powdery product, PP-O-Mg-CI-BF3 complex, is dried under vacuum for several hours. A sample of a complex formed from the PP-OH, Grignard reagent and BF3 in this manner was subjected to structure characterization~0 and was found to have an Mg:B:F atom ratio of 1:1:3.
Oligomeri7~tion of 1-Octene with C~talyst Complex from PP-OH. Grignard Reagent ~nd Roron Trifluoride ~ C~lyst A series of 12 consecutive oligomerization reactions was conducted in 25 which the same 1 gram sample of PP-O-Mg-CI-BF3 complex produced as in Example 5 was recovered by filtration after each run in a dry box and reused in the next run, a procedure that was repeated over and over again rn I
throughout the entire series. In each run powdery soJid complex and 10 r,~
of fresh 1-octene were charged to an air-free 50 ~ flask and the mixture 30 was heated up to 60~C for the desired reaction time. After each run the IENDED SHE~;, IP~AIEP
W O 97/21651 PCT~US96/19988 oligomer-containing reaction product was filtered to separate the catalyst complex from the liquid oligomer-containing phase for use in the next run.
The separated liquid phase was distilled under vacuum to remove unreacted 1-octene monomer. Elemental analysis of the recovered catalyst after the 5 last run of the series showed that almost no change in BF3 concentration in the catalyst occurred after 12 reaction cycles. Table 5 summarizes the conditions used and the results obtained in these 12 runs. Table 6 summarizes analytical data concerning the composition of some of the oligomers formed in these runs.
Table 5 Run No. Re~ion R~eno~ Ti~, Product Yield, Col~vc.~on, Temp., ~C hr. g 1 60 2 1.62 22.7 2 60 2 1.84 Z5.7 3 60 2 1.74 24.3 4 60 2 1.78 24.9 3 2.45 34.2 6 60 4 3.04 42.5 7 60 2 1.72 24.1 8 60 2 1.85 25.8 9 60 2 1.74 24.3 2 1.80 25.1 11 60 3 2.29 32.0 12 60 4 3.10 43.3 W O97/21651 PCT~US96/19988 Table 6 ~un No. D~ner, % Tr~ner, % Teo~mer, % P~u~uue~, %
3 55.5 42.5 2.0 none 8 58.3 40.7 1.0 none 0 The entire disciosure of each and every U.S. patent and each and every technical publication referred to in any portion of this specification is incorporated herein by reference for all purposes.
This invention is susceptible to considerable variation in its practice.
Therefore the foregoing description is not intended to limit, and shouid not be construed as limiting, the invention to the particular exemplifications presented hereinabove. Rather, what is intended to be covered is as set forth in the ensuing claims and the equivalents thereof permitted as a matter of law.
Claims
We claim:
1. A process of preparing alpha-olefin oligomer which comprises oligomerizing at least one oligomerizable 1-olefin having in the range of about 8 to about 20 carbon atoms per molecule by contacting said 1-olefin with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) a boron trihalide, and, (iii) an organomagnesium halide.
2. A process according to Claim 1 wherein the catalyst system is formed by charging said solid olefin polymer having pendant omega-hydroxyalkyl groups, boron trihalide and organomagnesium halide to said oligomerizable 1-olefin.
3. A process according to Claim 1 wherein the catalyst system is a complex formed from said solid olefin polymer having pendant omega-hydroxyalkyl groups, said organomagnesium halide and said boron trihalide. 4. A process according to any of Claims 1-3 wherein said oligomerizable 1-olefin has about 8 to about 14 carbon atoms per molecule and said boron trihalide is boron trifluoride.
5. A process according to any of Claims 1-4 wherein said solid olefin polymer is a poly(1-alkene-co-1-alken-~-ol) polymer in which the alkene units contain 3 to about 10 carbon atoms each and the 1-alken-~-ol units contain 6 to about 12 carbon atoms each.
6. A process according to any of Claims 1, 2, 4 and 5 wherein the oligomerization is conducted in a series of two or more separate oligomerization reactions which comprises:
a) conducting a first oligomerization reaction by contacting the oligomerizable 1-olefin with a catalyst system formed from (i) a solid olefin polymer having a linear backbone a plurality of pendant omega-hydroxyalkyl groups, and (ii) a boron trihalide and (iii) an organomagnesium halide, whereby the oligomerization results in a reaction mixture comprising a liquid alpha-olefin oligomer phase and a solids phase comprising solid olefin polymer catalyst residue;
b) separating said liquid phase and said solids phase from each other; and c) conducting another said reaction by contacting oligomerizable 1-olefin with a catalyst system formed from (i) said separated solids phase and (ii) a fresh charge of a boron trihalide.
7. A process according to any of Claims 1 and 3-5 wherein the oligomerization is conducted in a series of two or more separate oligomerization reactions which comprises:
a) conducting a first oligomerization reaction by contacting the oligomerizable 1-olefin with a heterogeneous catalyst complex formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) an organomagnesium halide and (iii) a boron trihalide, whereby the oligomerization results in a reaction mixture comprising a liquid alpha-olefin oligomer phase and a solids phase comprising solid olefin polymer catalyst residue;
b) separating said liquid phase and said solids phase from each other; and c) conducting another said reaction by contacting oligomerizable 1-olefin with said solids phase as catalyst.
8. A catalyst composition comprising a solid olefin polymer having a linear backbone with at least one pendant group comprising a moiety composed of magnesium, boron, halogen and oxygen and an alkyl group linking said moiety to said backbone.
9. A catalyst composition comprising a solid complex formed by a process comprising reacting an organomagnesium halide and a solid olefin polymer having pendant omega hydroxyalkyl groups in an inert, anhydrous liquid medium to form an intermediate product and reacting said product with a boron trihalide in an inert, anhydrous liquid medium.
10. A process of preparing alpha-olefin oligomer which comprises oligomerizing at least one oligomerizable 1-olefin having in the range of about 8 to about 20 carbon atoms per molecule by contacting said 1-olefin with a catalyst composition according to Claim 8 or 9.
1. A process of preparing alpha-olefin oligomer which comprises oligomerizing at least one oligomerizable 1-olefin having in the range of about 8 to about 20 carbon atoms per molecule by contacting said 1-olefin with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) a boron trihalide, and, (iii) an organomagnesium halide.
2. A process according to Claim 1 wherein the catalyst system is formed by charging said solid olefin polymer having pendant omega-hydroxyalkyl groups, boron trihalide and organomagnesium halide to said oligomerizable 1-olefin.
3. A process according to Claim 1 wherein the catalyst system is a complex formed from said solid olefin polymer having pendant omega-hydroxyalkyl groups, said organomagnesium halide and said boron trihalide. 4. A process according to any of Claims 1-3 wherein said oligomerizable 1-olefin has about 8 to about 14 carbon atoms per molecule and said boron trihalide is boron trifluoride.
5. A process according to any of Claims 1-4 wherein said solid olefin polymer is a poly(1-alkene-co-1-alken-~-ol) polymer in which the alkene units contain 3 to about 10 carbon atoms each and the 1-alken-~-ol units contain 6 to about 12 carbon atoms each.
6. A process according to any of Claims 1, 2, 4 and 5 wherein the oligomerization is conducted in a series of two or more separate oligomerization reactions which comprises:
a) conducting a first oligomerization reaction by contacting the oligomerizable 1-olefin with a catalyst system formed from (i) a solid olefin polymer having a linear backbone a plurality of pendant omega-hydroxyalkyl groups, and (ii) a boron trihalide and (iii) an organomagnesium halide, whereby the oligomerization results in a reaction mixture comprising a liquid alpha-olefin oligomer phase and a solids phase comprising solid olefin polymer catalyst residue;
b) separating said liquid phase and said solids phase from each other; and c) conducting another said reaction by contacting oligomerizable 1-olefin with a catalyst system formed from (i) said separated solids phase and (ii) a fresh charge of a boron trihalide.
7. A process according to any of Claims 1 and 3-5 wherein the oligomerization is conducted in a series of two or more separate oligomerization reactions which comprises:
a) conducting a first oligomerization reaction by contacting the oligomerizable 1-olefin with a heterogeneous catalyst complex formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) an organomagnesium halide and (iii) a boron trihalide, whereby the oligomerization results in a reaction mixture comprising a liquid alpha-olefin oligomer phase and a solids phase comprising solid olefin polymer catalyst residue;
b) separating said liquid phase and said solids phase from each other; and c) conducting another said reaction by contacting oligomerizable 1-olefin with said solids phase as catalyst.
8. A catalyst composition comprising a solid olefin polymer having a linear backbone with at least one pendant group comprising a moiety composed of magnesium, boron, halogen and oxygen and an alkyl group linking said moiety to said backbone.
9. A catalyst composition comprising a solid complex formed by a process comprising reacting an organomagnesium halide and a solid olefin polymer having pendant omega hydroxyalkyl groups in an inert, anhydrous liquid medium to form an intermediate product and reacting said product with a boron trihalide in an inert, anhydrous liquid medium.
10. A process of preparing alpha-olefin oligomer which comprises oligomerizing at least one oligomerizable 1-olefin having in the range of about 8 to about 20 carbon atoms per molecule by contacting said 1-olefin with a catalyst composition according to Claim 8 or 9.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/572,278 US5811617A (en) | 1995-12-13 | 1995-12-13 | Olefin oligomerization process |
US08/572,278 | 1995-12-13 | ||
US08/572,224 US5945574A (en) | 1995-12-13 | 1995-12-13 | Olefin oligomerization process and catalysts therefor |
US08/572,224 | 1995-12-13 |
Publications (1)
Publication Number | Publication Date |
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CA2239182A1 true CA2239182A1 (en) | 1997-06-19 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA 2239182 Abandoned CA2239182A1 (en) | 1995-12-13 | 1996-12-13 | Olefin oligomerization process and catalyst |
Country Status (4)
Country | Link |
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EP (1) | EP0866784A1 (en) |
JP (1) | JP2000502084A (en) |
CA (1) | CA2239182A1 (en) |
WO (1) | WO1997021651A1 (en) |
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WO2010117028A1 (en) * | 2009-04-10 | 2010-10-14 | 出光興産株式会社 | Α-olefin ologimer and method for producing same |
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US5288677A (en) * | 1991-06-28 | 1994-02-22 | Exxon Chemical Patents Inc. | Immobilized Lewis acid catalysts |
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1996
- 1996-12-13 JP JP9522249A patent/JP2000502084A/en active Pending
- 1996-12-13 CA CA 2239182 patent/CA2239182A1/en not_active Abandoned
- 1996-12-13 EP EP96944392A patent/EP0866784A1/en not_active Withdrawn
- 1996-12-13 WO PCT/US1996/019988 patent/WO1997021651A1/en not_active Application Discontinuation
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WO1997021651A1 (en) | 1997-06-19 |
EP0866784A1 (en) | 1998-09-30 |
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