WO2004046209A1 - Transition metal catalysts for producing polyvinyl esters - Google Patents
Transition metal catalysts for producing polyvinyl esters Download PDFInfo
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- WO2004046209A1 WO2004046209A1 PCT/EP2003/012538 EP0312538W WO2004046209A1 WO 2004046209 A1 WO2004046209 A1 WO 2004046209A1 EP 0312538 W EP0312538 W EP 0312538W WO 2004046209 A1 WO2004046209 A1 WO 2004046209A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 229920001290 polyvinyl ester Polymers 0.000 title claims description 9
- 229910052723 transition metal Inorganic materials 0.000 title claims description 5
- 150000003624 transition metals Chemical class 0.000 title claims description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000004646 arylidenes Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 12
- 229920001567 vinyl ester resin Polymers 0.000 abstract description 11
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- -1 s-pentyl Chemical group 0.000 description 49
- 238000006116 polymerization reaction Methods 0.000 description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000003780 insertion Methods 0.000 description 6
- 230000037431 insertion Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002689 polyvinyl acetate Polymers 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
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- 125000002091 cationic group Chemical group 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- BPOZNMOEPOHHSC-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCOC(=O)C=C BPOZNMOEPOHHSC-UHFFFAOYSA-N 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- YFDAMRSZJLWUSQ-UHFFFAOYSA-N tris(2-methylphenyl)borane Chemical compound CC1=CC=CC=C1B(C=1C(=CC=CC=1)C)C1=CC=CC=C1C YFDAMRSZJLWUSQ-UHFFFAOYSA-N 0.000 description 1
- LKNHGIFPRLUGEG-UHFFFAOYSA-N tris(3,4,5-trifluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC(B(C=2C=C(F)C(F)=C(F)C=2)C=2C=C(F)C(F)=C(F)C=2)=C1 LKNHGIFPRLUGEG-UHFFFAOYSA-N 0.000 description 1
- OHSAEOPCBBOWPU-UHFFFAOYSA-N tris(3,5-dimethylphenyl)borane Chemical compound CC1=CC(C)=CC(B(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 OHSAEOPCBBOWPU-UHFFFAOYSA-N 0.000 description 1
- YPVVTWIAXFPZLS-UHFFFAOYSA-N tris(4-fluorophenyl)borane Chemical compound C1=CC(F)=CC=C1B(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 YPVVTWIAXFPZLS-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- OSMBUUFIZBTSNO-UHFFFAOYSA-N tris[4-(fluoromethyl)phenyl]borane Chemical compound C1=CC(CF)=CC=C1B(C=1C=CC(CF)=CC=1)C1=CC=C(CF)C=C1 OSMBUUFIZBTSNO-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
Definitions
- Transition metal catalysts for the production of polyvinyl esters are Transition metal catalysts for the production of polyvinyl esters
- the present invention relates to catalysts for polymerization
- Copolymerization of vinyl esters and a process for the polymerization and copolymerization of vinyl esters.
- Vinyl esters are olefinic compounds with the following basic structure.
- Polyvinyl esters are polymers accessible from vinyl esters by olefinic polymerization, of which the polyvinyl acetates are by far the largest technical
- Polyvinyl acetate is an important thermoplastic polymer and is used, among other things, as an adhesive (component), raw material for coatings, for packaging films, for the coating of paper and food (sausage and cheese coatings)
- polyvinyl acetate is produced by free radical polymerizations, the polymerization being able to be carried out in solution, in bulk and in emulsion.
- Azoisobutyronitrile and dibenzoyl peroxide (AIBN / BPO) are mainly used as radical initiators. Since these radical polymerizations take place quickly and in an uncontrolled manner, stereodifferentiation is ruled out and control of the molecular weight and the molecular weight distribution very difficult (W. Daniels in.. Kirk-Othmer encycl Chem Technol, 3rd Ed 1983, 23, 817-847.).
- the transition metal allows catalyzed insertion polymerization with so-called metallocene or post-metallocene synthesis of stereospecific polymers having a narrow molecular weight distribution (W. Kaminsky in Ullmann's Encyclopedia of Industrial Chemistry, 6 th Ed., 2002 Electronic Release, Wiley / VCH).
- catalysts with a suitable ligand structure have now been found which not only permit the simple insertion of vinyl esters, but also multiple insertion up to the formation of the polymer.
- the present invention relates to compounds of the formula I.
- M 1 is a transition metal of the 3rd to 12th group of the periodic table of the
- Elements means whose oxidation state is not equal to zero, preferably the 8th to 10th group, particularly preferably nickel or palladium, and
- R 1 is hydrogen or a Ci - C 2 o- carbon-containing group or
- R 2 is hydrogen or a Ci - C 2 o- carbon-containing group or
- Is halogen and is an integer between 1 and 4, and is an integer between 1 and 4, and
- L 1 is in each case identical or different and has a mono- or bidentate ligand
- Is donor atoms of the 14th to 16th group of elements preferably of the following basic structure
- X 1 is in each case the same or different, and is an element from the 14th to 16th group of elements, particularly preferably nitrogen or phosphorus, and
- X 2 is in each case the same or different, and an element of the 14th to 16th group of the elements, particularly preferably nitrogen or phosphorus, and R 3 is in each case the same or different, and is hydrogen or a Ci - C 2 o
- X 1 is a carbon-containing group, and when X 1 is nitrogen preferably a substituted arylidene or aryl group or when X 1 is phosphorus preferably a substituted aryl group and
- R 4 is in each case the same or different, and is hydrogen or a Ci - C 2 o - carbon-containing group, and if X 2 is nitrogen preferably a substituted arylidene or aryl group or if X 2 is phosphorus preferably a substituted aryl group Is group and R 5 is in each case the same or different, and is hydrogen or a Ci - C 2 o
- - is a carbon-containing group and can also form a cyclic system with R 6 or R 7 , and
- R 6 is in each case the same or different, and is hydrogen or a Ci - C 2 o
- - is a carbon-containing group and can also form a cyclic system with R 5 or R 7 , and
- R 7 is in each case identical or different and is hydrogen or a Ci - C 2 o - carbon-containing group, and can also form a cyclic system with R 5 or R 6 , and m is 0, 1 or 2, and n is equal Is 0, 1 or 2, and o is an integer from 0 to 20, preferably 0 to 10 and particularly preferably is 0, 1 or 2, and p is in each case identical or different and is 1 or 2, and q is the same or different and is 1 or 2, and r is the same or different and is 1 or 2.
- Ci in the context of the present invention
- - C 2 o carbon-containing group is preferably the radicals -C 2 -alkyl, particularly preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl , t-butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl or cyclooctyl, Ci - C 2 o - alkenyl, particularly preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, Cyclohexenyl, octenyl or cyclooctenyl, Ci - C 2 o - alkynyl, particularly preferably ethynyl, propyn
- C 4 -C 2 o-heterocycloalkyl particularly preferably furyl, benzofuryl, 2-pyrolidinyl, 2-indolyl, 3-indolyl, 2,3-dihydroindolyl, C 8 -C 2 o-arylalkenyl, particularly preferably o-vinylphenyl, m- vinylphenyl, p-vinylphenyl, C 8 -C 2 o-arylalkynyl, particularly preferably o-ethynylphenyl, m-ethynylphenyl or p-ethynylphenyl, C 2 - C 2 o - heteroatom-containing group, particularly preferably carbonyl, benzoyl, oxybenzoyl, benzoyloxy, acetyl .
- Acetoxy or nitrile understood, where one or more C 1 -C 2 o-carbon-containing groups can form a cyclic system.
- n 1 -5
- Ph may be the same or different and may be a phenyl, a substituted phenyl group such as tolyl or methoxyphenyl, a fluorinated phenyl, or an oxyphenyl, or another substituted aromatic radical and can also be an alkyl or oxyalkyl radical.
- iodaniline is reacted with diphenylphosphine to form the corresponding aminoarylphosphino compound under palladium catalysis.
- the corresponding ligand is then built up in a condensation reaction with a benzaldehyde derivative, which is then reacted directly with the desired metal species to form a catalyst according to the invention.
- the compounds of the formula I according to the invention are suitable as catalysts for the preparation of polyvinyl esters.
- Another component of the present invention are compounds of formula II, which is formed from a compound of formula I by conversion with vinyl esters.
- R 8 is the same or different and is hydrogen or a Ci - C 2 o- carbon-containing group
- R 9 is hydrogen or a Ci - C 2 o - carbon-containing group
- X 3 is a non-coordinating anion
- s is either an integer 1 or 2
- t is an integer between 1 and 3
- u is an integer between 1 and 3
- v is an integer between 1 and 3
- w is a is an integer between 1 and 3 where t multiplied by u is always equal to v multiplied by w, and the other radicals have the meaning defined under formula I, except for the compound of formula A.
- X 3 preferably means those composed of mixtures of several atoms of the elements aluminum, boron, antimony, arsenic, nitrogen, carbon, phosphorus, sulfur, oxygen, chlorine and fluorine. In the context of this invention, this is particularly preferably understood to mean fluorinated or perfluorinated Ci - C 2 o -carbon-containing groups.
- Illustrative, but not limiting, examples of this are: tetraphenylborate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, tetrakis (dimethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (3,5-bis-trifluoromethylphenyl) borate, tetrakis (tetrakis) , Tetrakis (4-fluorophenyl) borate, tetrakis (pentafluoropheny!)
- a cationic complex is first produced by the addition of a silver salt by abstraction of the chloride ion.
- this cationic complex inserts, for example, a molecule of vinyl acetate and thus forms a complex of the formula II.
- Another component of the present invention is a process for the polymerization of vinyl esters using the catalyst or catalyst system according to the invention, polymerization being understood to mean both the homopolymerization of vinyl esters and the copolymerization of vinyl esters with other olefins.
- Examples of other olefins are 1-olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norbornadiene, ethyl norbomadiene and cyclic olefins such as norbornene, cyclopentadiene, tetracyclododecene or methyl norbomene, and polar monomers such as methyl acrylate, methyl methacrylate, acrylic acid, acrylic acid, acrylic acid -Butyl acrylate and 2-ethylhexyl acrylate.
- Vinyl acetate is preferably homopolymerized in the process according to the invention, or vinyl acetate with one or more 1-olefins having 2 to 8 carbon atoms, such as
- the polymerization can optionally be carried out either with an additive of the formula III or without an additional additive:
- M 2 is the same or different and is a metal of the 1st to 14th group of the
- Periodic table is, preferably lithium, magnesium, scandium, titanium, boron, aluminum, silicon, tin, particularly preferably boron and aluminum, and R 9 is the same or different and is hydrogen, a halogen atom or a Ci
- the additives of the formula III optionally used according to the invention are one or more compounds of the type of an aluminoxane and / or another Lewis acid.
- the polymerization is carried out at a temperature of from -20 to 300 ° C., preferably from 0 to
- the polymerization can be carried out in solution, in bulk, in suspension or in emulsion, continuously or batchwise, in one or more stages.
- Suitable solvents for the polymerization are, for example, aliphatic hydrocarbons such as pentane,
- the cocatalyst of the formula III which together with at least one compound of the formula I or formula II according to the invention can form the catalyst system, contains at least one compound of the aluminoxane or Lewis acid type.
- cocatalysts which can form the catalyst system together with a compound of the formula I or formula II are: aluminoxanes, for example in JACS 117 (1995), 6465-74 and Organometallics 13 (1994), 2957-2969 are described, or Lewis acids, which consist, for example, of boron or organoaluminium compounds, or cocatalysts, which are described in EP-A-924223, DE-A-19622207, EP-A-601830, EP-A-824112, EP-A -8241 13, EP-A-81 1627, WO97 / 1 1775 and DE-A-19606167.
- Lewis acids are those which contain at least one or more atoms of lithium, magnesium, scandium, titanium, boron, aluminum, silicon and / or tin. It is particularly preferred to use at least one organoboron or organoaluminum compound which contains C1-C20 carbon-containing groups, such as branched or unbranched alkyl or
- Haloalkyl such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl, such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di (trifluoromethyl) phenyl.
- unsaturated groups such as aryl or haloaryl, such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di (trifluoromethyl) phenyl.
- aryl or haloaryl such as phenyl, to
- Tris (3,5-difluorophenyl) borane Tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3,5-dimethylphenyl) borane, tris (3,5-difluorophenyl) borane, Tris (3,4,5-trifluorophenyl) borane.
- the carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g. highly porous polyolefins, such as
- polar polymers such as. e.g. Polyurethanes, polymethacrylates, polymethyl methacrylates, polyvinyl acetate, polyacrylonitrile, polyethylene glycol or copolymers).
- Suitable inorganic oxides can be found in the II. VI. Main group of the
- Periodic table and the lll.-IV. Subgroup of the Periodic Table of the Elements examples include silicon dioxide, hydrotalcite, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures.
- preferred oxides as carriers include silicon dioxide, hydrotalcite, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures.
- Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxidic supports are, for example, MgO, ZrO 2 , TiO 2 or B 2 O 3 , to name just a few. The invention is illustrated by the following examples which, however, do not restrict the invention.
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Abstract
The invention relates to novel compounds that can be used as catalysts for polymerizing and copolymerizing vinyl esters. The invention also relates to a method for polymerizing and copolymerizing vinyl esters while using these compounds.
Description
Celanese Ventures GmbHCelanese Ventures GmbH
Übergangsmetall-Katalysatoren zur Herstellung von PolyvinylesternTransition metal catalysts for the production of polyvinyl esters
Die vorliegende Erfindung betrifft Katalysatoren zur Polymerisation undThe present invention relates to catalysts for polymerization and
Copolymensation von Vinylestern sowie ein Verfahren zur Polymerisation und Copolymensation von Vinylestern.Copolymerization of vinyl esters and a process for the polymerization and copolymerization of vinyl esters.
Vinylester sind olefinische Verbindungen mit der folgenden Grundstruktur.Vinyl esters are olefinic compounds with the following basic structure.
Vertreter dieser Verbindungsklasse sind beispielsweise Vinylacetat (R = CH3), Ben- zoesäurevinylester (R = Ph), Vinylformiat (R = H), Vinylpropionat (R = C2Hs), Pivalin- säurevinylester (R = tB ), Vinylhexanoat (R = C5H11), Vinyllaurat (R = CnH23). Polyvinylester sind durch olefinische Polymerisation aus Vinylestern zugängliche Polymere, von denen die Polyvinylacetate die mit Abstand größte technischeRepresentatives of this class of compounds are, for example, vinyl acetate (R = CH 3 ), benzoic acid vinyl ester (R = Ph), vinyl formate (R = H), vinyl propionate (R = C 2 Hs), pivalic acid vinyl ester (R = tB), vinyl hexanoate (R = C5H11), vinyl laurate (R = CnH 23 ). Polyvinyl esters are polymers accessible from vinyl esters by olefinic polymerization, of which the polyvinyl acetates are by far the largest technical
Bedeutung haben.Have meaning.
Polyvinylacetat ist ein wichtiges thermoplastisches Polymer und wird unter anderem als Klebstoff(komponente), Lackrohstoff, für Verpackungsfolien, für die Beschichtungen von Papier und Lebensmitteln (Wurst- u. Käsebeschichtungen), alsPolyvinyl acetate is an important thermoplastic polymer and is used, among other things, as an adhesive (component), raw material for coatings, for packaging films, for the coating of paper and food (sausage and cheese coatings)
Additiv für Beton und als Rohstoff für die Herstellung von Polyvinylalkoholen und Polyvinylacetalen verwendet (Römpp Lexikon Chemie - Version 2.0, Stuttgart/New York: Georg Thieme Verlag 1999).Used as an additive for concrete and as a raw material for the production of polyvinyl alcohols and polyvinyl acetals (Römpp Lexikon Chemie - Version 2.0, Stuttgart / New York: Georg Thieme Verlag 1999).
In der Technik wird Polyvinylacetat durch freie radikalische Polymerisationen hergestellt, wobei die Polymerisation in Lösung, in Masse und in Emulsion durchgeführt werden kann. Als Radikalstarter dienen hierbei vorwiegend Azoisobutyronitril und Dibenzoylperoxid (AIBN / BPO). Da diese radikalischen Polymerisationen schnell und unkontrolliert ablaufen, ist eine Stereodifferenzierung ausgeschlossen und eine Kontrolle des Molekulargewichtes und der Molekular-
gewichtsverteilung nur schwer möglich (W. Daniels in: Kirk-Othmer Encycl. Chem. TechnoL, 3rd Ed. 1983, 23, 817-847).In the art, polyvinyl acetate is produced by free radical polymerizations, the polymerization being able to be carried out in solution, in bulk and in emulsion. Azoisobutyronitrile and dibenzoyl peroxide (AIBN / BPO) are mainly used as radical initiators. Since these radical polymerizations take place quickly and in an uncontrolled manner, stereodifferentiation is ruled out and control of the molecular weight and the molecular weight distribution very difficult (W. Daniels in.. Kirk-Othmer encycl Chem Technol, 3rd Ed 1983, 23, 817-847.).
Aufgrund der Beschränkung auf eine radikalische Polymerisation von Vinylacetat ist es bislang noch nicht gelungen, Polyvinylacetate stereospezifisch mit einer schmalen Molekulargewichtsverteilung zu synthetisieren. Polymere mit spezieller Stereochemie auf der Basis anderer Monomere finden aufgrund ihrer besonderen Eigenschaften beispielsweise Anwendungen als Ersatzstoffe für teurere Polymere oder kompliziertere Polymermischungen.Because of the restriction to radical polymerization of vinyl acetate, it has not yet been possible to synthesize polyvinyl acetates in a stereospecific manner with a narrow molecular weight distribution. Polymers with special stereochemistry based on other monomers are used, for example, as substitutes for more expensive polymers or more complicated polymer mixtures due to their special properties.
Im Gegensatz zur freien radikalischen Polymerisation ermöglicht die Übergangsmetall katalysierte Insertions-Polymerisation mit sogenannten Metallocenen oder Post-Metallocenen die Synthese von stereospezifischen Polymeren mit enger Molekulargewichtsverteilung (W. Kaminsky in Ullmann's Encyclopedia of Industrial Chemistry, 6th Ed., 2002 Electronic Release, Wiley/VCH).In contrast to the free radical polymerization, the transition metal allows catalyzed insertion polymerization with so-called metallocene or post-metallocene synthesis of stereospecific polymers having a narrow molecular weight distribution (W. Kaminsky in Ullmann's Encyclopedia of Industrial Chemistry, 6 th Ed., 2002 Electronic Release, Wiley / VCH).
Diese Methode wurde bislang für viele meist einfache α-Olefine erfolgreich angewandt. Der Einsatz von polaren Monomeren ist bei dieser Methode bisher auf einige Acrylate beschränkt (WO0121670). Die Polymerisation von Vinylacetat durch eine Übergangsmetall katalysierte Insertions-Polymerisation mit Metallocenen oder Post-Metallocenen gelang jedoch bisher nicht.This method has been used successfully for many mostly simple α-olefins. With this method, the use of polar monomers has hitherto been restricted to a few acrylates (WO0121670). However, the polymerization of vinyl acetate by a transition metal-catalyzed insertion polymerization with metallocenes or post-metallocenes has so far not been possible.
Eine einmalige Insertion von Vinylacetat in eine Übergangsmetall-Kohlenstoff Bindung wurde in der Literatur für einen Palladium-Komplex mit einem Phosphin-Imin Liganden beschrieben (Liu et al. Organomβtallics 1999, 18, 2574). Eine weitere Insertion von Vinylacetat und eine damit verbundene Polyvinylacetat Bildung gelang jedoch nicht.A single insertion of vinyl acetate into a transition metal-carbon bond has been described in the literature for a palladium complex with a phosphine-imine ligand (Liu et al. Organomβtallics 1999, 18, 2574). However, a further insertion of vinyl acetate and the associated formation of polyvinyl acetate did not succeed.
Überraschenderweise wurden nun Katalysatoren mit einer geeigneten Liganden- Struktur gefunden, welche nicht nur die einfache Insertion von Vinylestern erlauben, sondern auch die mehrfache Insertion bis hin zur Polymerbildung.
Gegenstand der vorliegenden Erfindung sind Verbindungen der Formel ISurprisingly, catalysts with a suitable ligand structure have now been found which not only permit the simple insertion of vinyl esters, but also multiple insertion up to the formation of the polymer. The present invention relates to compounds of the formula I.
Formel IFormula I.
worin: M1 ein Übergangsmetall der 3. bis 12. Gruppe des Periodensystems derwherein: M 1 is a transition metal of the 3rd to 12th group of the periodic table of the
Elemente bedeutet dessen Oxidationstufe ungleich null ist, bevorzugt der 8. bis 10. Gruppe, besonders bevorzugt Nickel oder Palladium ist, undElements means whose oxidation state is not equal to zero, preferably the 8th to 10th group, particularly preferably nickel or palladium, and
R1 gleich Wasserstoff oder eine Ci - C2o- kohlenstoffhaltige Gruppe oder einR 1 is hydrogen or a Ci - C 2 o- carbon-containing group or
Halogenatom ist, undIs halogen atom, and
R2 gleich Wasserstoff oder eine Ci - C2o- kohlenstoffhaltige Gruppe oder einR 2 is hydrogen or a Ci - C 2 o- carbon-containing group or
Halogenatom ist, und eine ganze natürliche Zahl zwischen 1 und 4 ist, und eine ganze natürliche Zahl zwischen 1 und 4 ist, undIs halogen, and is an integer between 1 and 4, and is an integer between 1 and 4, and
L1 jeweils gleich oder verschieden ist und ein mono- oder bidentater Ligand mitL 1 is in each case identical or different and has a mono- or bidentate ligand
Donoratomen der 14. bis 16. Gruppe der Elemente ist, bevorzugt von folgender GrundstrukturIs donor atoms of the 14th to 16th group of elements, preferably of the following basic structure
ist, und
X1 jeweils gleich oder verschieden ist, und ein Element der 14. bis 16. Gruppe der Elemente, besonders bevorzugt Stickstoff oder Phosphor ist, undis and X 1 is in each case the same or different, and is an element from the 14th to 16th group of elements, particularly preferably nitrogen or phosphorus, and
X2 jeweils gleich oder verschieden ist, und ein Element der 14. bis 16. Gruppe der Elemente, besonders bevorzugt Stickstoff oder Phosphor ist, und R3 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine Ci - C2oX 2 is in each case the same or different, and an element of the 14th to 16th group of the elements, particularly preferably nitrogen or phosphorus, and R 3 is in each case the same or different, and is hydrogen or a Ci - C 2 o
- kohlenstoffhaltige Gruppe ist, und wenn X1 gleich Stickstoff bevorzugt eine substituierte Aryliden- oder Aryl-Gruppe oder wenn X1 gleich Phosphor bevorzugt eine substituierte Aryl-Gruppe ist undis a carbon-containing group, and when X 1 is nitrogen preferably a substituted arylidene or aryl group or when X 1 is phosphorus preferably a substituted aryl group and
R4 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine Ci - C2o - kohlenstoffhaltige Gruppe ist, und wenn X2 gleich Stickstoff bevorzugt eine substituierte Aryliden- oder Aryl-Gruppe ist oder wenn X2 gleich Phosphor bevorzugt eine substituierte Aryl-Gruppe ist und R5 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine Ci - C2oR 4 is in each case the same or different, and is hydrogen or a Ci - C 2 o - carbon-containing group, and if X 2 is nitrogen preferably a substituted arylidene or aryl group or if X 2 is phosphorus preferably a substituted aryl group Is group and R 5 is in each case the same or different, and is hydrogen or a Ci - C 2 o
- kohlenstoffhaltige Gruppe ist, und mit R6 oder R7 auch ein cyclisches System bilden kann, und- is a carbon-containing group and can also form a cyclic system with R 6 or R 7 , and
R6 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine Ci - C2oR 6 is in each case the same or different, and is hydrogen or a Ci - C 2 o
- kohlenstoffhaltige Gruppe ist, und mit R5 oder R7 auch ein cyclisches System bilden kann, und- is a carbon-containing group and can also form a cyclic system with R 5 or R 7 , and
R7 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine Ci - C2o - kohlenstoffhaltige Gruppe ist, und mit R5 oder R6 auch ein cyclisches System bilden kann, und m gleich 0, 1 oder 2 ist, und n gleich 0, 1 oder 2 ist, und o eine ganze natürliche Zahl von 0 bis 20 ist, bevorzugt 0 bis 10 und besonders bevorzugt gleich 0, 1 oder 2 ist, und p jeweils gleich oder verschieden ist, und gleich 1 oder 2 ist, und q jeweils gleich oder verschieden ist, und gleich 1 oder 2 ist, und r jeweils gleich oder verschieden ist, und gleich 1 oder 2 ist.R 7 is in each case identical or different and is hydrogen or a Ci - C 2 o - carbon-containing group, and can also form a cyclic system with R 5 or R 6 , and m is 0, 1 or 2, and n is equal Is 0, 1 or 2, and o is an integer from 0 to 20, preferably 0 to 10 and particularly preferably is 0, 1 or 2, and p is in each case identical or different and is 1 or 2, and q is the same or different and is 1 or 2, and r is the same or different and is 1 or 2.
Im Rahmen der vorliegenden Erfindung werden unter einer Ci - C2o -kohlenstoffhaltigen Gruppe bevorzugt die Reste CrC2o-Alkyl, besonders bevorzugt Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, s-Butyl, t-Butyl, n-Pentyl, s-Pentyl, Cyclopentyl, n-Hexyl, Cyclohexyl, n-Octyl oder Cyclooctyl, Ci - C2o - Alkenyl, besonders bevorzugt Ethenyl, Propenyl, Butenyl, Pentenyl, Cyclopentenyl, Hexenyl,
Cyclohexenyl, Octenyl oder Cyclooctenyl, Ci - C2o - Alkinyl, besonders bevorzugt Ethinyl, Propinyl, Butinyl, Pentinyl, Hexinyl oder Octinyl, C6-C2o-Aryl, besonders bevorzugt Benzyliden, o-Methoxybenzyliden, 2,6-Dimethylbenzyliden, Phenyl, Biphenyl, Naphthyl oder Anthracenyl, Ci - C2o - Fluoralkyl, besonders bevorzugt Trifluormethyl, Pentafluorethyl oder 2,2,2-Trifluorethyl, C6-C2o-Aryl, besonders bevorzugt Phenyl, Biphenyl, Naphthyl, Anthracenyl, Triphenylenyl, [1 ,1';3,,1"]Terphenyl-2,-yl, Binaphthyl oder Phenanthrenyl, C6-C2o-Fluoraryl, besonders bevorzugt Pentafluorophenyl, 3,5-Bistrifluoromethylphenyl, Pentafluorobenzyliden, 3,5-Bistrifluoromethylbenzyliden, Tetrafluorophenyl oder Heptafluoronaphthyl, C-ι-C20-Alkoxy, besonders bevorzugt Methoxy, Ethoxy, n-Are a Ci in the context of the present invention - C 2 o carbon-containing group is preferably the radicals -C 2 -alkyl, particularly preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl , t-butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl or cyclooctyl, Ci - C 2 o - alkenyl, particularly preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, Cyclohexenyl, octenyl or cyclooctenyl, Ci - C 2 o - alkynyl, particularly preferably ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl, C 6 -C 2 o-aryl, particularly preferably benzylidene, o-methoxybenzylidene, 2,6-dimethylbenzylidene , Phenyl, biphenyl, naphthyl or anthracenyl, Ci - C 2 o - fluoroalkyl, particularly preferably trifluoromethyl, pentafluoroethyl or 2,2,2-trifluoroethyl, C 6 -C 2 o-aryl, particularly preferably phenyl, biphenyl, naphthyl, anthracenyl, triphenylenyl, [1, 1 '; 3, 1 "] terphenyl-2-yl, binaphthyl or phenanthrenyl, C 6 -C 2 o-fluoroaryl, more preferably pentafluorophenyl, 3,5-Bistrifluoromethylphenyl, Pentafluorobenzyliden, 3,5- Bistrifluoromethylbenzylidene, tetrafluorophenyl or heptafluoronaphthyl, C 1 -C 20 alkoxy, particularly preferably methoxy, ethoxy, n-
Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy oder t-Butoxy, C6-C2o-Aryloxy, besonders bevorzugt Phenoxy, Naphthoxy, Biphenyloxy, Anthracenyloxy, Phenanthrenyloxy, C7-C20-Arylalkyl, besonders bevorzugt o-Tolyl, m-Tolyl, p-Tolyl, 2,6-Dimethylphenyl, 2,6-Diethylphenyl, 2,6-Di-i-propylphenyl, 2,6-Di-t-butylphenyl, o- t-Butylphenyl, m-t-Butylphenyl, p-t-Butylphenyl, C7-C2o-Alkylaryl, besonders bevorzugt Benzyl, Ethylphenyl, Propylphenyl, Diphenylmethyl, Triphenylmethyl oder Naphthalinylmethyl, C7-C20-Aryloxyalkyl, besonders bevorzugt o-Methoxyphenyl, m- Phenoxymethyl, p-Phenoxymethyl, Cι2-C2o-Aryloxyaryl, besonders bevorzugt p- Phenoxyphenyl, C5-C20-Heteroaryl, besonders bevorzugt 2-Pyridyl, 3-Pyridyl, 4- Pyridyl, Chinolinyl, Isochinolinyl, Acridinyl, Benzochinolinyl oder Benzoisochinolinyl,Propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy or t-butoxy, C 6 -C 20 aryloxy, particularly preferably phenoxy, naphthoxy, biphenyloxy, anthracenyloxy, phenanthrenyloxy, C 7 -C 20 arylalkyl, particularly preferably o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-i-propylphenyl, 2,6-di-t-butylphenyl, o-t-butylphenyl , mt-butylphenyl, pt-butylphenyl, C 7 -C 2 o-alkylaryl, particularly preferably benzyl, ethylphenyl, propylphenyl, diphenylmethyl, triphenylmethyl or naphthalinylmethyl, C 7 -C 20 aryloxyalkyl, particularly preferably o-methoxyphenyl, m-phenoxymethyl, p-Phenoxymethyl, C 2 -C 2 o-aryloxyaryl, particularly preferably p-phenoxyphenyl, C 5 -C 20 heteroaryl, particularly preferably 2-pyridyl, 3-pyridyl, 4-pyridyl, quinolinyl, isoquinolinyl, acridinyl, benzoquinolinyl or benzoisoquinolinyl .
C4-C2o-Heterocycloalkyl, besonders bevorzugt Furyl, Benzofuryl, 2-Pyrolidinyl, 2- Indolyl, 3-lndolyl, 2,3-Dihydroindolyl, C8-C2o-Arylalkenyl, besonders bevorzugt o- Vinylphenyl, m-Vinylphenyl, p-Vinylphenyl, C8-C2o-Arylalkinyl, besonders bevorzugt o-Ethinylphenyl, m-Ethinylphenyl oder p-Ethinylphenyl, C2 - C2o - heteroatomhaltige Gruppe, besonders bevorzugt Carbonyl, Benzoyl, Oxybenzoyl, Benzoyloxy, Acetyl,C 4 -C 2 o-heterocycloalkyl, particularly preferably furyl, benzofuryl, 2-pyrolidinyl, 2-indolyl, 3-indolyl, 2,3-dihydroindolyl, C 8 -C 2 o-arylalkenyl, particularly preferably o-vinylphenyl, m- vinylphenyl, p-vinylphenyl, C 8 -C 2 o-arylalkynyl, particularly preferably o-ethynylphenyl, m-ethynylphenyl or p-ethynylphenyl, C 2 - C 2 o - heteroatom-containing group, particularly preferably carbonyl, benzoyl, oxybenzoyl, benzoyloxy, acetyl .
Acetoxy oder Nitril verstanden, wobei eine oder mehrere Cι-C2o-kohlenstoffhaltige Gruppen ein cyclisches System bilden können.Acetoxy or nitrile understood, where one or more C 1 -C 2 o-carbon-containing groups can form a cyclic system.
Erläuternde, die Erfindung jedoch nicht einschränkende Beispiele für Verbindungen der Formel I sind:
Illustrative but non-limiting examples of compounds of formula I are:
In den vorstehend aufgeführten Beispielen für Verbindungen der Formel I kann aus Gründen der Vereinfachung Ph gleich oder verschieden sein und eine Phenyl-, eine substituierte Phenylgruppe wie Tolyl oder Methoxyphenyl, eine fluorierte Phenyl-, oder eine Oxyphenyl-, oder ein anderer substituierter aromatischer Rest sowie auch ein Alkyl- oder Oxyalkyl-Rest sein.
In the examples of compounds of the formula I given above, for the sake of simplicity, Ph may be the same or different and may be a phenyl, a substituted phenyl group such as tolyl or methoxyphenyl, a fluorinated phenyl, or an oxyphenyl, or another substituted aromatic radical and can also be an alkyl or oxyalkyl radical.
Die Synthese der erfindungsgemäßen Verbindungen der Formel I kann nach allgemein bekannten Verfahren durchgeführt werden. Ein Beispiel hierfür ist im folgenden aufgeführt.The synthesis of the compounds of formula I according to the invention can be carried out by generally known methods. An example of this is shown below.
Hierzu wird in einem ersten Schritt lodanilin unter Palladium-Katalyse mit Diphenylphosphin zur entsprechenden Aminoarylphosphino-Verbindung umgesetzt. In einer Kondensationsreaktion mit einem Benzaldehyd-Derivat wird dann der entsprechende Ligand aufgebaut, welcher anschließend direkt mit der gewünschten Metallspezies zu einem erfindungsgemäßen Katalysator umgesetzt wird.For this purpose, iodaniline is reacted with diphenylphosphine to form the corresponding aminoarylphosphino compound under palladium catalysis. The corresponding ligand is then built up in a condensation reaction with a benzaldehyde derivative, which is then reacted directly with the desired metal species to form a catalyst according to the invention.
Die erfindungsgemäßen Verbindungen der Formel I eignen sich als Katalysator zur Herstellung von Polyvinylestern.
The compounds of the formula I according to the invention are suitable as catalysts for the preparation of polyvinyl esters.
Weiterer Bestandteil der vorliegenden Erfindung sind Verbindungen der Formel II, welche aus einer Verbindung der Formel I durch Umsatz mit Vinylestern gebildet wird.Another component of the present invention are compounds of formula II, which is formed from a compound of formula I by conversion with vinyl esters.
Formel II worin:Formula II in which:
R8 gleich oder verschieden ist, und gleich Wasserstoff oder eine Ci - C2o- kohlenstoffhaltige Gruppe ist, und R9 gleich Wasserstoff oder eine Ci - C2o - kohlenstoffhaltige Gruppe ist, und X3 ein nicht-koordinierendes Anion bedeutet, und s entweder eine ganze natürliche Zahl 1 oder 2 ist, und t eine ganze natürliche Zahl zwischen 1 und 3 ist, und u eine ganze natürliche Zahl zwischen 1 und 3 ist, und v eine ganze natürliche Zahl zwischen 1 und 3 ist, und w eine ganze natürliche Zahl zwischen 1 und 3 ist, wobei t multipliziert mit u immer gleich v multipliziert mit w ist, und die anderen Reste die unter Formel I definierte Bedeutung haben, ausgenommen die Verbindung der Formel AR 8 is the same or different and is hydrogen or a Ci - C 2 o- carbon-containing group, and R 9 is hydrogen or a Ci - C 2 o - carbon-containing group, and X 3 is a non-coordinating anion, and s is either an integer 1 or 2, and t is an integer between 1 and 3, and u is an integer between 1 and 3, and v is an integer between 1 and 3, and w is a is an integer between 1 and 3, where t multiplied by u is always equal to v multiplied by w, and the other radicals have the meaning defined under formula I, except for the compound of formula A.
Formel A
Diese Verbindung kann optional isoliert und im weiteren Verfahren eingesetzt werden.Formula A This connection can optionally be isolated and used in the further process.
Im Rahmen der vorliegenden Erfindung werden unter nicht-koordinierenden AnionenIn the context of the present invention are among non-coordinating anions
X3 bevorzugt solche aus Gemischen von mehreren Atomen der Elemente Aluminium, Bor, Antimon, Arsen, Stickstoff, Kohlenstoff, Phosphor, Schwefel, Sauerstoff, Chlor und Fluor verstanden. Besonders bevorzugt werden darunter im Rahmen dieser Erfindung fluorierte oder perfluorierte Ci - C2o- kohlenstoffhaltige Gruppen verstanden. Erläuternde, die Erfindung jedoch nicht einschränkende Beispiele hierfür sind: Tetraphenylborat, Tetrafluoroborat, Tetrakis(pentafluorphenyl)borat, Tetrakis(dimethylphenyl)borat, Tetrakis(tolyl)borat, Tetrakis(3,5-bis- trifluormethylphenyl)borat, Tetrakis(trifluormethylphenyl)borat, Tetrakis(4- fluorphenyl)borat, Tetrakis(pentafluoropheny!)aluminat, Hexafluoroantimonat, Hexafluoroarsenat, Hexafluorophosphat, Thiocyanat, Chlorat, Tetrachloroaluminat oder Heptachlorodialuminat.X 3 preferably means those composed of mixtures of several atoms of the elements aluminum, boron, antimony, arsenic, nitrogen, carbon, phosphorus, sulfur, oxygen, chlorine and fluorine. In the context of this invention, this is particularly preferably understood to mean fluorinated or perfluorinated Ci - C 2 o -carbon-containing groups. Illustrative, but not limiting, examples of this are: tetraphenylborate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, tetrakis (dimethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (3,5-bis-trifluoromethylphenyl) borate, tetrakis (tetrakis) , Tetrakis (4-fluorophenyl) borate, tetrakis (pentafluoropheny!) Aluminate, hexafluoroantimonate, hexafluoroarsenate, hexafluorophosphate, thiocyanate, chlorate, tetrachloroaluminate or heptachlorodialuminate.
Die Synthese der erfindungsgemäßen Katalysatoren nach Formel II kann nach allgemein bekannten Verfahren wie z. B. in Angew. Chem. Int. Ed. 1999, 38, 428-447 beschrieben durchgeführt werden. Je nach eingesetztem Katalysator ist eineThe synthesis of the catalysts of the formula II according to the invention can be carried out by generally known methods such as. B. in Angew. Chem. Int. Ed. 1999, 38, 428-447. Depending on the catalyst used, one is
Alkylierung sowie auch eine Aktivierung der Katalysatoren mit allgemein bekannten Reagenzien (siehe auch Formel III) der Bildung von Verbindungen der Formel II vorgeschaltet.Alkylation and also an activation of the catalysts with generally known reagents (see also formula III) preceded the formation of compounds of formula II.
Ein Beispiel 1 für eine die Erfindung nicht einschränkende Umsetzung eines erfindungsgemäßen Katalysators der Formel I ist im folgenden aufgeführt.An example 1 for a reaction of a catalyst of the formula I according to the invention which does not restrict the invention is listed below.
Ein weiterer Bestandteil der vorliegenden Erfindung ist ein Verfahren zur Polymerisation von Vinylestern unter Verwendung des erfindungsgemäßen Katalysators oder Katalysatorsystems, wobei unter Polymerisation sowohl die Homopolymerisation von Vinylestern als auch die Copolymensation von Vinylestern mit anderen Olefinen verstanden wird. Beispiele für andere Olefine sind 1-Olefine mit 2 - 20, vorzugsweise 2 bis 10 C-Atomen, wie Ethen, Propen, 1-Buten, 1-Penten, 1- Hexen, 1-Decen, 4-Methyl-1-penten oder 1-Octen, Styrol, Diene wie 1 ,3-Butadien, 1 ,4-Hexadien, Vinylnorbornen, Norbornadien, Ethylnorbomadien und cyclische Olefine wie Norbornen, Cyclopentadien, Tetracyclododecen oder Methylnorbomen, und polare Monomere wie Methylacrylat, Methylmethacrylat, Acrylsäure, Ethylacrylat, n-Butylacrylat und 2-Ethylhexylacrylat.Another component of the present invention is a process for the polymerization of vinyl esters using the catalyst or catalyst system according to the invention, polymerization being understood to mean both the homopolymerization of vinyl esters and the copolymerization of vinyl esters with other olefins. Examples of other olefins are 1-olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norbornadiene, ethyl norbomadiene and cyclic olefins such as norbornene, cyclopentadiene, tetracyclododecene or methyl norbomene, and polar monomers such as methyl acrylate, methyl methacrylate, acrylic acid, acrylic acid, acrylic acid -Butyl acrylate and 2-ethylhexyl acrylate.
Bevorzugt wird in dem erfindungsgemäßen Verfahren Vinylacetat homopolymerisiert, oder Vinylacetat mit einem oder mehreren 1 -Olefinen mit 2 bis 8 C-Atomen, wieVinyl acetate is preferably homopolymerized in the process according to the invention, or vinyl acetate with one or more 1-olefins having 2 to 8 carbon atoms, such as
Ethen, Propen, Styrol, Norbornen, Methylacrylat, Methylmethacrylat, Acrylsäure oder Butadien copolymerisiert.Copolymerized ethene, propene, styrene, norbornene, methyl acrylate, methyl methacrylate, acrylic acid or butadiene.
Die Polymerisation kann je nach Katalysator optional bevorzugt sowohl mit einem Additiv der Formel III als auch ohne ein zusätzliches Additiv durchgeführt werden:Depending on the catalyst, the polymerization can optionally be carried out either with an additive of the formula III or without an additional additive:
Formel IIIFormula III
worin M2 jeweils gleich oder verschieden ist und ein Metall der 1. bis 14. Gruppe deswherein M 2 is the same or different and is a metal of the 1st to 14th group of the
Periodensystems ist, bevorzugt Lithium, Magnesium, Scandium, Titan, Bor, Aluminium, Silicium, Zinn, besonders bevorzugt Bor und Aluminium, und
R9 gleich oder verschieden ist und Wasserstoff, ein Halogenatom oder eine CiPeriodic table is, preferably lithium, magnesium, scandium, titanium, boron, aluminum, silicon, tin, particularly preferably boron and aluminum, and R 9 is the same or different and is hydrogen, a halogen atom or a Ci
C2o - kohlenstoffhaltige Gruppe, und x eine ganze natürliche Zahl zwischen 1 und 5 ist, und y eine ganze natürliche Zahl zwischen 1 und 5 ist, und z eine ganze natürliche Zahl zwischen 1 und 5 ist.C 2 o - carbon-containing group, and x is an integer between 1 and 5, and y is an integer between 1 and 5, and z is an integer between 1 and 5.
Dabei ist bei Verwendung von Verbindungen der Formel II mit einem am Imin gebundenen unsubstituierten Aromaten zur Polymerisation der Zusatz von Additiven der Formel III zwingend erforderlich. Ein Beispiel einer solchen Verbindung ist im folgenden abgebildet.When using compounds of the formula II with an unsubstituted aromatic bonded to the imine, the addition of additives of the formula III is imperative for the polymerization. An example of such a connection is shown below.
Bei allen anderen erfindungsgemäßen Verbindungen der Formeln I bzw. II ist die Verwendung eines Additivs der Formel III optional möglich.For all other compounds of the formulas I and II according to the invention, the use of an additive of the formula III is optionally possible.
Bei den erfindungsgemäß optional verwendeten Additiven der Formel III handelt es sich um eine oder mehrere Verbindungen des Typs eines Aluminoxans oder/und einer anderen Lewis-Säure.The additives of the formula III optionally used according to the invention are one or more compounds of the type of an aluminoxane and / or another Lewis acid.
Die Polymerisation wird bei einer Temperatur von -20 bis 300°C, bevorzugt 0 bisThe polymerization is carried out at a temperature of from -20 to 300 ° C., preferably from 0 to
200°C, ganz besonders bevorzugt bei 20 bis 100°C durchgeführt. Der Druck beträgt 0.5 bis 2000 bar, bevorzugt 1 bis 64 bar. Die Polymerisation kann in Lösung, in Masse, in Suspension oder in Emulsion, kontinuierlich oder diskontinuierlich, ein- oder mehrstufig durchgeführt werden. Geeignete Lösungsmittel für die Polymerisation sind beispielsweise aliphatische Kohlenwasserstoffe wie Pentan,200 ° C, very particularly preferably carried out at 20 to 100 ° C. The pressure is 0.5 to 2000 bar, preferably 1 to 64 bar. The polymerization can be carried out in solution, in bulk, in suspension or in emulsion, continuously or batchwise, in one or more stages. Suitable solvents for the polymerization are, for example, aliphatic hydrocarbons such as pentane,
Hexan und dergleichen oder aromatische Kohlenwasserstoffe wie Benzol, Toluol, Xylole und dergleichen, oder Ether wie Diethylether, Dibutylether, Methyl-tert- butylether, Tetra hydrofu ran, Dioxan, Anisol, Diphenylether und Ethylphenylether,
auch halogenierte Lösungsmittel wie Dichlormethan, Trichlormethan, Chlorbenzol, Brombenzol und dergleichen, sowie Ethylacetat, Aceton, N,N-Dimethylformamid, Ethylencarbonat, Methanol, Ethanol, Propanol, i-Propanol oder Wasser. Es können auch Mischungen verschiedener Lösungsmittel in unterschiedlichen Mengenverhältnissen erfindungsgemäß eingesetzt werden.Hexane and the like or aromatic hydrocarbons such as benzene, toluene, xylenes and the like, or ethers such as diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, anisole, diphenyl ether and ethylphenyl ether, also halogenated solvents such as dichloromethane, trichloromethane, chlorobenzene, bromobenzene and the like, and also ethyl acetate, acetone, N, N-dimethylformamide, ethylene carbonate, methanol, ethanol, propanol, i-propanol or water. Mixtures of different solvents in different proportions can also be used according to the invention.
Der Cokatalysator der Formel III, der zusammen mit mindestens einer erfindungsgemäßen Verbindung der Formel I oder Formel II das Katalysatorsystem bilden kann, enthält mindestens eine Verbindung vom Typ eines Aluminoxans oder einer Lewis-Säure. Die Cokatalysatoren, die zusammen mit einer Verbindung derThe cocatalyst of the formula III, which together with at least one compound of the formula I or formula II according to the invention can form the catalyst system, contains at least one compound of the aluminoxane or Lewis acid type. The cocatalysts, which together with a compound of
Formel I oder Formel II das erfindungsgemäße Katalysatorsystem bilden können, sind in WO 0148034 beschrieben. Die erfindungsgemäßen Katalysatorsysteme, welche aus einer Verbindung der Formel I oder Formel II und den in WO 0148034 beschriebenen Cokatalysatoren gebildet werden kann, werden ebenfalls von der vorliegenden Erfindung mit umfasst.Formula I or Formula II that can form the catalyst system according to the invention are described in WO 0148034. The catalyst systems according to the invention, which can be formed from a compound of the formula I or formula II and the cocatalysts described in WO 0148034, are also included in the present invention.
Erläuternde, jedoch nicht einschränkende Beispiele für Cokatalysatoren, die zusammen einer Verbindung der Formel I oder Formel II das Katalysatorsystem bilden können, sind: Aluminoxane, die beispielsweise in JACS 117 (1995), 6465-74 und Organometallics 13 (1994), 2957-2969 beschrieben werden, oder Lewis-Säuren, die beispielsweise aus bor- oder aluminiumorganischen Verbindungen bestehen, oder Cokatalysatoren, die in EP-A-924223, DE-A-19622207, EP-A-601830, EP-A- 824112, EP-A-8241 13, EP-A-81 1627, WO97/1 1775 und DE-A-19606167 beschrieben sind.Illustrative but non-limiting examples of cocatalysts which can form the catalyst system together with a compound of the formula I or formula II are: aluminoxanes, for example in JACS 117 (1995), 6465-74 and Organometallics 13 (1994), 2957-2969 are described, or Lewis acids, which consist, for example, of boron or organoaluminium compounds, or cocatalysts, which are described in EP-A-924223, DE-A-19622207, EP-A-601830, EP-A-824112, EP-A -8241 13, EP-A-81 1627, WO97 / 1 1775 and DE-A-19606167.
Als Lewis-Säuren werden erfindungsgemäß optional solche eingesetzt, welche mindestens eins oder mehrere Atome von Lithium, Magnesium, Scandium, Titan, Bor, Aluminium, Silicium und/oder Zinn enthalten. Besonders bevorzugt wird mindestens eine bor- oder aluminiumorganische Verbindung eingesetzt, die C1-C20- kohlenstoffhaltige Gruppen enthält, wie verzweigte oder unverzweigte Alkyl- oderAccording to the invention, Lewis acids optionally used are those which contain at least one or more atoms of lithium, magnesium, scandium, titanium, boron, aluminum, silicon and / or tin. It is particularly preferred to use at least one organoboron or organoaluminum compound which contains C1-C20 carbon-containing groups, such as branched or unbranched alkyl or
Halogenalkyl, wie z.B. Methyl, Propyl, Isopropyl, Isobutyl, Trifluormethyl, ungesättigte Gruppen, wie Aryl oder Halogenaryl, wie Phenyl, Tolyl, Benzylgruppen, p- Fluorophenyl, 3,5-Difluorophenyl, Pentachlorophenyl, Pentafluorophenyl, 3,4,5- Trifluorophenyl und 3,5-Di(trifluoromethyl)phenyl.
Erläuternde, die Erfindung jedoch nicht einschränkende Beispiele für die optional eingesetzten Cokatalysatoren sind:Haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl, such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di (trifluoromethyl) phenyl. Illustrative but non-limiting examples of the optionally used cocatalysts are:
Trimethylaluminium, Triethylaluminium, Triisobutylaluminium, Tributylaluminium, Trifluoroboran, Triphenylboran, Tris(4-fluorophenyl)boran,Trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tributyl aluminum, trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane,
Tris(3,5-difluorophenyl)boran, Tris(4-fluoromethylphenyl)boran, Tris(pentafluorophenyl)boran, Tris(tolyl)boran, Tris(3,5-dimethylphenyl)boran, Tris(3,5-difluorophenyl)boran, Tris(3,4,5-trifluorophenyl)boran. ClAI(Me)2, AI(OMe)3, AI(OEt)3, AI(O-t7Pr)3, AI(O-/Pr)3, AI(O-nBu)3, AI(O-sBu)3, AI(O- .Bu)3) MeAI(O-2,6-di-foutylphenyl)2, AI(O-2,6-di-foutylphenyl)3, TiCI4, Ti(OMe)4,Tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3,5-dimethylphenyl) borane, tris (3,5-difluorophenyl) borane, Tris (3,4,5-trifluorophenyl) borane. ClAI (Me) 2 , AI (OMe) 3 , AI (OEt) 3 , AI (O-t7Pr) 3 , AI (O- / Pr) 3 , AI (O-nBu) 3 , AI (O-sBu) 3 , AI (O- .Bu) 3) MeAI (O-2,6-di-foutylphenyl) 2 , AI (O-2,6-di-foutylphenyl) 3 , TiCI 4 , Ti (OMe) 4 ,
Ti(OEt)4, Ti(O-/?Pr)4, Ti(O-/Pr)4, Ti(O-/7Bu)4, Ti(O-sBu)4, Ti(O-fBu)4, Sc(OTf)3, MgBr2, SiCI4, SnCI4) LiCIO4) LiOMe, LiOEt, LiO-πPr, LiO-/Pr, LiO-nBu, LiO-sBu, LiO-fBu, BCI3, B(Et)3, B(Ph)3, B(OMe)3, B(OPh)3, B(OEt)3, B(O-t?Pr)3, B(O-/Pr)3, B(O-nBu)3, B(O-sBu)3, B(O-u3u)3.Ti (OEt) 4 , Ti (O - /? Pr) 4 , Ti (O- / Pr) 4 , Ti (O- / 7Bu) 4 , Ti (O-sBu) 4 , Ti (O-fBu) 4 , Sc (OTf) 3 , MgBr 2 , SiCI 4 , SnCI 4) LiCIO 4) LiOMe, LiOEt, LiO-πPr, LiO- / Pr, LiO-nBu, LiO-sBu, LiO-fBu, BCI 3 , B (Et) 3 , B (Ph) 3 , B (OMe) 3 , B (OPh) 3 , B (OEt) 3 , B (Ot? Pr) 3 , B (O- / Pr) 3 , B (O-nBu) 3 , B (O-sBu) 3 , B (O-u3u) 3 .
Desweiteren können die erfindungsgemäßen Katalysatoren homogen und auch heterogen geträgert eingesetzt werden. Die Trägerkomponente des erfindungsgemäßen Katalysatorsystems kann ein beliebiger organischer oder anorganischer, inerter Feststoff sein, insbesondere ein poröser Träger wie Talk, anorganische Oxide und feinteilige Polymerpulver (z.B. hochporöse Polyolefine, wieFurthermore, the catalysts of the invention can be used homogeneously and also heterogeneously supported. The carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g. highly porous polyolefins, such as
Polyethylen, Polypropylen, Polystyrole, Copolymere, oder polare Polymere, wie. z.B. Polyurethane, Polymethacrylate, Polymethylmethacrylate, Polyvinylacetat, Polyacrylonitril, Polyethylenglycol oder Copolymere).Polyethylene, polypropylene, polystyrenes, copolymers, or polar polymers, such as. e.g. Polyurethanes, polymethacrylates, polymethyl methacrylates, polyvinyl acetate, polyacrylonitrile, polyethylene glycol or copolymers).
Geeignete anorganische Oxide finden sich in der II. -VI. Hauptgruppe desSuitable inorganic oxides can be found in the II. VI. Main group of the
Periodensystems und der lll.-IV. Nebengruppe des Periodensystems der Elemente. Beispiele für als Träger bevorzugte Oxide umfassen Siliciumdioxid, Hydrotalcit, Aluminiumoxid, sowie Mischoxide der Elemente Calcium, Aluminium, Silicium, Magnesium, Titan und entsprechende Oxid-Mischungen. Andere anorganische Oxide, die allein oder in Kombination mit den zuletzt genannten bevorzugten oxidischen Trägern eingesetzt werden können, sind z.B. MgO, ZrO2, TiO2 oder B2O3, um nur einige zu nennen.
Die Erfindung wird durch folgende, die Erfindung jedoch nicht einschränkende Beispiele erläutert.Periodic table and the lll.-IV. Subgroup of the Periodic Table of the Elements. Examples of preferred oxides as carriers include silicon dioxide, hydrotalcite, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures. Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxidic supports are, for example, MgO, ZrO 2 , TiO 2 or B 2 O 3 , to name just a few. The invention is illustrated by the following examples which, however, do not restrict the invention.
Allgemeine Angaben: Die Herstellung und Handhabung der organometallischen Verbindungen erfolgte unter Ausschluß von Luft und Feuchtigkeit unter Argon- Schutzgas (Schlenk-Technik bzw. Glove-Box). Alle benötigten Lösemittel wurden vor Gebrauch mit Argon gespült und über Molsieb absolutiert.General information: The production and handling of the organometallic compounds was carried out with the exclusion of air and moisture under an argon protective gas (Schlenk technique or glove box). All required solvents were flushed with argon before use and absoluteized using a molecular sieve.
Beispiel 1 : Synthese des Katalysators 1Example 1: Synthesis of catalyst 1
In einem ausgeheizten Schlenkrohr werden 522 mg (1.0 mmol) [2-Methoxy- benzyliden-(2-diphenylphosphanyl-phenyl)-amin]-methylpalladium(ll)chlorid in 20 ml abs. Dichlormethan gelöst. Anschließend werden langsam 195 mg (1.0 mmol) AgBF4 in 10 ml trockenem Acetonitril zugegeben. Nach 1 h Rühren bei Raumtemperatur wird der entstandene Niederschlag unter Schutzgas über Celite abfiltriert und das Lösungsmittel wird auf 2 ml reduziert. Abschließend werden zu dieser Lösung 20 ml abs. Diethylether gegeben und das Produkt unter Schutzgas über eine ausgeheizte Fritte abfiltriert. In einem ausgeheizten Kolben werden 100 mg (0.15 mmol) des aktiviertenIn a heated Schlenk tube, 522 mg (1.0 mmol) of [2-methoxybenzylidene (2-diphenylphosphanylphenyl) amine] methylpalladium (II) chloride in 20 ml of abs. Dichloromethane dissolved. Then 195 mg (1.0 mmol) of AgBF 4 in 10 ml of dry acetonitrile are slowly added. After stirring for 1 h at room temperature, the precipitate formed is filtered off under protective gas over Celite and the solvent is reduced to 2 ml. Finally, 20 ml abs. Given diethyl ether and the product filtered off under protective gas over a heated frit. In a heated flask, 100 mg (0.15 mmol) of the activated
Komplexes in 5 ml abs. CH2CI2 gelöst und mit 10 ml (0.11 mol) Vinylacetat versetzt. Diese Mischung wird bei 40°C für 20 h gerührt.Complex in 5 ml abs. CH 2 CI 2 dissolved and mixed with 10 ml (0.11 mol) of vinyl acetate. This mixture is stirred at 40 ° C for 20 h.
Anschließend wird die Lösung unter Schutzgas über Celite filtriert. Das Filtrat wird im Vakuum bis auf ca. 2 ml eingeengt und mit 20 ml abs. Diethylether versetzt. Das ausfallende Produkt wird unter Schutzgas abfiltriert und verbleibt nach Trocknung als farbloser Feststoff.
Ausbeute: 600 mg (90 %). H-NMR (500 MHz, CDCI3): δ = 9.40 (s, 1 H, CHN), 8.20 - 8.10 (m, 4H, arom. H), 7.75 - 7.00 (m, 14H, arom. H), 5.35 (m, 1 H, PdCH), 3,95 (s, 3H, OCH3), 2.07 (s, 3H, CO2CH3), 1.70 - 1.50 (m, 2H, CH2), 0.98 (t, 3H, CH3) ppm.The solution is then filtered through Celite under protective gas. The filtrate is concentrated in vacuo to about 2 ml and with 20 ml abs. Diethyl ether added. The product which precipitates is filtered off under protective gas and remains after drying as a colorless solid. Yield: 600 mg (90%). H-NMR (500 MHz, CDCI 3 ): δ = 9.40 (s, 1 H, CHN), 8.20 - 8.10 (m, 4H, aromatic H), 7.75 - 7.00 (m, 14H, aromatic H), 5.35 (m, 1 H, PdCH), 3.95 (s, 3H, OCH 3 ), 2.07 (s, 3H, CO 2 CH 3 ), 1.70 - 1.50 (m, 2H, CH 2 ), 0.98 (t, 3H , CH 3 ) ppm.
Beispiel 2: Polymerisation von Vinylacetat mit dem Katalysator 1Example 2: Polymerization of vinyl acetate with catalyst 1
In einem ausgeheizten Kolben werden unter Schutzgas 22 mg (32 μmol) Katalysator 1 gegeben und mit 10 ml abs. Toluol versetzt. Anschließend werden 16 μl (32 μmol) Trimethylaluminium (2 M in Toluol) zugesetzt und es wird für eine Stunde bei22 mg (32 μmol) of catalyst 1 are added to a heated flask under protective gas and 10 ml of abs. Toluene added. Then 16 μl (32 μmol) trimethyl aluminum (2 M in toluene) are added and it is left for one hour
Raumtemperatur gerührt. Nun erfolgt die Zugabe von 1.85 ml frisch destilliertem Vinylacetat und es wird für zwölf Stunden bei Raumtemperatur gerührt. Danach wird die Reaktion durch Zugabe von 2 ml saurem Methanol gestoppt und das Gemisch auf 1 ml Restvolumen eingeengt. Durch Zugabe von 20 ml Heptan wird das entstandene Polymer gefällt und die überstehende Lösung wird abdekantiert. DerRoom temperature stirred. Now 1.85 ml of freshly distilled vinyl acetate are added and the mixture is stirred at room temperature for twelve hours. The reaction is then stopped by adding 2 ml of acidic methanol and the mixture is concentrated to a residual volume of 1 ml. The polymer formed is precipitated by adding 20 ml of heptane and the supernatant solution is decanted off. The
Rückstand wird im Ölpumpenvakuum getrocknet. Ausbeute: 240 mg (2.79 mmol, 14%). 1H-NMR (500 MHz, CDCI3): δ = 4.86 (bs, 1H, CH), 2.01 (bt, 3H, COCH3), 1.75 (bd, 2H, CH2). 13C-NMR (500 MHz, CDCl3): δ = 170.4 - 170.0 (C=O), 68.5 - 66.5 (CH), 40.5 - 38.5 (CH2), 21.1 - 20.8 (CH3).
The residue is dried in an oil pump vacuum. Yield: 240 mg (2.79 mmol, 14%). 1 H NMR (500 MHz, CDCI 3 ): δ = 4.86 (bs, 1H, CH), 2.01 (bt, 3H, COCH 3 ), 1.75 (bd, 2H, CH 2 ). 13 C-NMR (500 MHz, CDCl 3 ): δ = 170.4 - 170.0 (C = O), 68.5 - 66.5 (CH), 40.5 - 38.5 (CH 2 ), 21.1 - 20.8 (CH 3 ).
Claims
Patentansprücheclaims
1. Verbindung der Formel I1. Compound of formula I.
Formel IFormula I.
worin:wherein:
M1 ein Übergangsmetall der 3. bis 12. Gruppe des Periodensystems derM 1 is a transition metal of the 3rd to 12th group of the periodic table of the
Elemente bedeutet dessen Oxidationstufe ungleich null ist, bevorzugt derElements means whose oxidation state is not equal to zero, preferably that
8. bis 10. Gruppe, besonders bevorzugt Nickel oder Palladium ist, und R1 gleich Wasserstoff oder eine C-ι - C20- kohlenstoffhaltige Gruppe oder ein8th to 10th group, particularly preferably nickel or palladium, and R 1 is hydrogen or a C 1 -C 20 carbon-containing group or a
Halogenatom ist, und R2 gleich Wasserstoff oder eine C^ - C20 - kohlenstoffhaltige Gruppe oder einIs halogen atom, and R 2 is hydrogen or a C ^ - C2 0 - carbon-containing group or
Halogenatom ist, und k eine ganze natürliche Zahl zwischen 1 und 4 ist, und I eine ganze natürliche Zahl zwischen 1 und 4 ist, und L1 jeweils gleich oder verschieden ist und ein mono- oder bidentater Ligand mit Donoratomen der 14. bis 16. Gruppe der Elemente ist, bevorzugt von folgender GrundstrukturIs a halogen atom, and k is an integer between 1 and 4, and I is an integer between 1 and 4, and L 1 is the same or different and is a mono- or bidentate ligand with donor atoms of 14th to 16th Group of elements is, preferably of the following basic structure
Gruppe der Elemente, besonders bevorzugt Stickstoff oder Phosphor ist, und X2 jeweils gleich oder verschieden ist, und ein Element der 14. bis 16.Group of elements, particularly preferably nitrogen or phosphorus, and X 2 is in each case the same or different, and an element of the 14th to 16th
Gruppe der Elemente, besonders bevorzugt Stickstoff oder Phosphor ist, und R3 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine Ci -Group of elements, particularly preferably nitrogen or phosphorus, and R 3 is in each case the same or different, and is hydrogen or a Ci -
C20- kohlenstoffhaltige Gruppe ist, und wenn X1 gleich Stickstoff bevorzugt eine substituierte Aryliden- oder Aryl-Gruppe oder wenn X1 gleich Phosphor bevorzugt eine substituierte Aryl-Gruppe ist und R4 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine C-ι -C 20 is a carbon-containing group, and when X 1 is nitrogen, preferably a substituted arylidene or aryl group, or when X 1 is phosphorus, preferably a substituted aryl group and R 4 is the same or different, and is hydrogen or a C. -ι -
C2o - kohlenstoffhaltige Gruppe ist, und wenn X2 gleich Stickstoff bevorzugt eine substituierte Aryliden- oder Aryl-Gruppe ist oder wenn X2 gleich Phosphor bevorzugt eine substituierte Aryl-Gruppe ist undC 2 o is a carbon-containing group, and if X 2 is nitrogen preferably a substituted arylidene or aryl group or if X 2 is phosphorus preferably a substituted aryl group and
R5 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine C-i -R 5 is in each case the same or different, and is hydrogen or a Ci -
C20 - kohlenstoffhaltige Gruppe ist, und mit R6 oder R7 auch ein cyclischesC2 0 - carbon-containing group, and a cyclic with R 6 or R 7
System bilden kann, und R6 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine C-i - C2o- kohlenstoffhaltige Gruppe ist, und mit R5 oder R7 auch ein cyclischesSystem can form, and R 6 is the same or different, and is hydrogen or a Ci - C 2 o carbon-containing group, and with R 5 or R 7 also a cyclic
System bilden kann, und R7 jeweils gleich oder verschieden ist, und gleich Wasserstoff oder eine C^i -System can form, and R 7 is each the same or different, and is hydrogen or a C ^ i -
C2o - kohlenstoffhaltige Gruppe ist, und mit R5 oder R6 auch ein cyclischesC 2 o is a carbon-containing group, and also a cyclic group with R 5 or R 6
System bilden kann, und m gleich 0, 1 oder 2 ist, und n gleich 0, 1 oder 2 ist, und 0 eine ganze natürliche Zahl von 0 bis 20 ist, bevorzugt 0 bis 10 und besonders bevorzugt gleich 0, 1 oder 2 ist, und p jeweils gleich oder verschieden ist, und gleich 1 oder 2 ist, und q jeweils gleich oder verschieden ist, und gleich 1 oder 2 ist, und r jeweils gleich oder verschieden ist, und gleich 1 oder 2 ist.
Verbindung der Formel IISystem can form, and m is 0, 1 or 2, and n is 0, 1 or 2, and 0 is an integer from 0 to 20, preferably 0 to 10 and particularly preferably 0, 1 or 2 , and p is each the same or different, and is 1 or 2, and q is each the same or different, and is 1 or 2, and r is each the same or different, and is 1 or 2. Compound of formula II
Formel II worin: R8 gleich oder verschieden ist, und gleich Wasserstoff oder eine C1 - C20 - kohlenstoffhaltige Gruppe ist, und R9 gleich Wasserstoff oder eine C1 - C20 - kohlenstoffhaltige Gruppe ist, und X3 ein nicht-koordinierendes Anion bedeutet, und s entweder eine ganze natürliche Zahl 1 oder 2 ist, und t eine ganze natürliche Zahl zwischen 1 und 3 ist, und u eine ganze natürliche Zahl zwischen 1 und 3 ist, und v eine ganze natürliche Zahl zwischen 1 und 3 ist, und w eine ganze natürliche Zahl zwischen 1 und 3 ist, wobei t multipliziert mit u immer gleich v multipliziert mit w ist, und die anderen Reste die in Anspruch 1 unter Formel I definierten Bedeutungen haben, ausgenommen die Verbindung der Formel AFormula II wherein: R8 is the same or different and is hydrogen or a C1 - C20 carbon group, and R9 is hydrogen or a C1 - C20 carbon group, and X3 is a non-coordinating anion, and s is either integer is 1 or 2, and t is an integer between 1 and 3, and u is an integer between 1 and 3, and v is an integer between 1 and 3, and w is an integer is between 1 and 3, where t multiplied by u is always equal to v multiplied by w, and the other radicals have the meanings defined in claim 1 under formula I, except for the compound of the formula A.
Formel A
Formula A
3. Katalysatorsystem enthaltend mindestens eine Verbindung der Formel II und mindestens einen Co-Katalysator der Formel III3. Catalyst system containing at least one compound of the formula II and at least one cocatalyst of the formula III
[(M2)x(R9)y]z [(M 2 ) x (R 9 ) y ] z
Formelformula
worinwherein
M2 jeweils gleich oder verschieden ist und ein Metall der 1. bis 14. Gruppe des Periodensystems ist, bevorzugt Lithium, Magnesium, Scandium, Titan, Bor, Aluminium, Silicium, Zinn, besonders bevorzugt Bor und Aluminium, undM2 is in each case identical or different and is a metal from the 1st to 14th group of the periodic table, preferably lithium, magnesium, scandium, titanium, boron, aluminum, silicon, tin, particularly preferably boron and aluminum, and
R9 gleich oder verschieden ist und Wasserstoff, ein Halogenatom oder eineR9 is the same or different and is hydrogen, a halogen atom or one
C1 - C20 - kohlenstoffhaltige Gruppe, und x eine ganze natürliche Zahl zwischen 1 und 5 ist, und y eine ganze natürliche Zahl zwischen 1 und 5 ist, und z eine ganze natürliche Zahl zwischen 1 und 5 ist.C1 - C20 - carbon-containing group, and x is an integer between 1 and 5, and y is an integer between 1 and 5, and z is an integer between 1 and 5.
4. Verwendung von mindestens einer Verbindung gemäß Anspruch 1 und/oder Anspruch 2 zur Herstellung von Polyvinylestern.4. Use of at least one compound according to claim 1 and / or claim 2 for the preparation of polyvinyl esters.
5. Verwendung von mindestens einem Katalysatorsystem gemäß Anspruch 3 zur5. Use of at least one catalyst system according to claim 3 for
Herstellung von Polyvinylestern.Manufacture of polyvinyl esters.
6. Verfahren zur Herstellung von Polyvinylestern, dadurch gekennzeichnet, daß mindestens eine Verbindung gemäß Anspruch 1 als Katalysator eingesetzt wird.6. A process for the preparation of polyvinyl esters, characterized in that at least one compound according to claim 1 is used as a catalyst.
7. Verfahren zur Herstellung von Polyvinylestern, dadurch gekennzeichnet, daß mindestens eine Verbindung gemäß Anspruch 2 als Katalysator eingesetzt wird.7. A process for the preparation of polyvinyl esters, characterized in that at least one compound according to claim 2 is used as a catalyst.
8. Verfahren zur Herstellung von Polyvinylestern, dadurch gekennzeichnet, daß mindestens eine Katalysatorsystem gemäß Anspruch 3 eingesetzt wird.
8. A process for the preparation of polyvinyl esters, characterized in that at least one catalyst system according to claim 3 is used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2002154093 DE10254093A1 (en) | 2002-11-20 | 2002-11-20 | Transition metal catalysts for the production of polyvinyl esters |
| DE10254093.4 | 2002-11-20 |
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| Publication Number | Publication Date |
|---|---|
| WO2004046209A1 true WO2004046209A1 (en) | 2004-06-03 |
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ID=32308601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2003/012538 WO2004046209A1 (en) | 2002-11-20 | 2003-11-11 | Transition metal catalysts for producing polyvinyl esters |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE10254093A1 (en) |
| WO (1) | WO2004046209A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0824111A1 (en) * | 1996-08-12 | 1998-02-18 | Elf Atochem S.A. | Process for radical controlled polymerization or copolymerization of (meth)acryl and vinyl monomers and thus prepared (co)polymers |
| WO2001021670A1 (en) * | 1999-09-20 | 2001-03-29 | The Penn State Research Foundation | Palladium (ii) catalyzed polymerization of norbornene and acrylates |
-
2002
- 2002-11-20 DE DE2002154093 patent/DE10254093A1/en not_active Withdrawn
-
2003
- 2003-11-11 WO PCT/EP2003/012538 patent/WO2004046209A1/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0824111A1 (en) * | 1996-08-12 | 1998-02-18 | Elf Atochem S.A. | Process for radical controlled polymerization or copolymerization of (meth)acryl and vinyl monomers and thus prepared (co)polymers |
| WO2001021670A1 (en) * | 1999-09-20 | 2001-03-29 | The Penn State Research Foundation | Palladium (ii) catalyzed polymerization of norbornene and acrylates |
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| Publication number | Publication date |
|---|---|
| DE10254093A1 (en) | 2004-06-09 |
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