EP3921352A1 - Bismuthaltiger katalysator umfassend mindestens einen aromatischen substituenten - Google Patents
Bismuthaltiger katalysator umfassend mindestens einen aromatischen substituentenInfo
- Publication number
- EP3921352A1 EP3921352A1 EP20701200.6A EP20701200A EP3921352A1 EP 3921352 A1 EP3921352 A1 EP 3921352A1 EP 20701200 A EP20701200 A EP 20701200A EP 3921352 A1 EP3921352 A1 EP 3921352A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- bismuth
- hydroxy
- substituents
- monosubstituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims description 74
- 125000003118 aryl group Chemical group 0.000 claims description 40
- -1 monosubstituted phenyl Chemical group 0.000 claims description 38
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 150000002367 halogens Chemical group 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000012634 fragment Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 150000001350 alkyl halides Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical group OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229940036348 bismuth carbonate Drugs 0.000 claims description 2
- XAEZALCLBRUCLR-UHFFFAOYSA-K bismuth;hydrogen carbonate Chemical compound [Bi+3].OC([O-])=O.OC([O-])=O.OC([O-])=O XAEZALCLBRUCLR-UHFFFAOYSA-K 0.000 claims description 2
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 150000001491 aromatic compounds Chemical class 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 82
- 239000003446 ligand Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- PYHXGXCGESYPCW-UHFFFAOYSA-N alpha-phenylbenzeneacetic acid Natural products C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- LSSYDKBADXXERA-UHFFFAOYSA-N 2,2-diphenyldecanoic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(CCCCCCCC)C1=CC=CC=C1 LSSYDKBADXXERA-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OGNSCSPNOLGXSM-UHFFFAOYSA-N (+/-)-DABA Natural products NCCC(N)C(O)=O OGNSCSPNOLGXSM-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- ODELFXJUOVNEFZ-UHFFFAOYSA-N 2,2-diphenylpropanoic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C)C1=CC=CC=C1 ODELFXJUOVNEFZ-UHFFFAOYSA-N 0.000 description 1
- BKSYWSWWJYBIRP-UHFFFAOYSA-N 2-ethylhexyl n-(6-isocyanatohexyl)carbamate Chemical compound CCCCC(CC)COC(=O)NCCCCCCN=C=O BKSYWSWWJYBIRP-UHFFFAOYSA-N 0.000 description 1
- WBJWXIQDBDZMAW-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(O)=CC=C21 WBJWXIQDBDZMAW-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101100443807 Pyrobaculum islandicum (strain DSM 4184 / JCM 9189 / GEO3) dpdh gene Proteins 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001210 attenuated total reflectance infrared spectroscopy Methods 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003086 colorant Substances 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
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 150000005599 propionic acid derivatives Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/54—Bismuth
Definitions
- a bismuth-containing catalyst comprising at least one aromatic substituent
- the invention relates to a bismut-containing catalyst as such which is defined by the general formula (I) set out in the following text.
- the bismut-containing catalyst contains at least one radical R 1 , which contains a carboxyl fragment according to the general formula (II), a first carbon atom ( ⁇ -carbon) being bonded to the carbon atom of the carboxyl group, which in turn according to the invention with at least one aromatic is directly substituted.
- the present invention further relates to a method for producing such a bismuth-containing catalyst and the use of such a bismuth-containing catalyst for producing compounds which contain a urethane group.
- WO 2018/069018 relates to a coating agent system which comprises components (A) to (C) and, if appropriate, further components.
- Component (A) is at least one compound containing polyhydroxy groups and component (B) is at least one compound containing polyisocyanate.
- component (C) is a catalyst which comprises at least two salts of an aliphatic monocarboxylic acid having at least 4 carbon atoms.
- the metal component of the first salt is bismuth (Bi), while the second salt has magnesium (Mg), sodium (Na), potassium (K) or calcium (Ca) as the metal component.
- the coating agent systems according to WO 2018/069018 can, according to a first option, be designed in such a way that all components are present separately from one another, i.e. the individual components are not mixed with one another, while according to a second option of the corresponding coating agent system the respective components are also completely or at least partially mixed with one another may exist.
- US Pat. No. 4,895,827 discloses a catalyst in the form of a metal salt, the catalyst being part of a thermally sensitive color-forming composition which, in addition to the catalyst, comprises a chromogenic material, an acidic developer and a suitable binder.
- the metal salt can contain different metals as the central metal atom / metal ion, including, for example, zinc, tin, aluminum or nickel.
- the corresponding metal salt contains organic compounds as ligands which, in addition to a carboxyl group, also include aromatic fragments and vinyl groups.
- bismuth-containing catalysts are not disclosed in US-A 4,895,827.
- JP-A 58 87 087 discloses the use of a polyvalent metal salt of diphenyl acetic acid, in particular of diphenyl zinc acetate, as a colorant, wherein a Waterproof colored image can be produced.
- Bismuth-containing metal salts or the use of metal salts for the production of a compound which contains a urethane bond are not disclosed in JP-A 58 87 087.
- the preparation of compounds containing a urethane group (urethane bond) has also been known for a long time.
- a compound having a urethane group is usually obtained if a compound having an isocyanate group is reacted with a compound having a hydroxyl group.
- the reaction is usually carried out in the presence of a catalyst.
- Tin-containing catalysts show a very high activity in such reactions, but the use of such tin-containing catalysts, in particular alkyl tin compounds, should be avoided because of their (very high) toxicity.
- R 1 is independently a radical of the general formula (II)
- R 2 is independently a radical of the general formula (III) O
- X is independently hydroxy, halogen, carbonate, hydrogen carbonate or R 7 and z is 0, 1 or 2; where the sum of x, y and z is 3;
- R 3 is unsubstituted or at least monosubstituted C 1 -C 4 -alkyl, C 6 -C 14 aryl or C 7 -C 30 aralkyl, the substituents being selected from hydroxy, halogen, carboxyl, -CF 3 , -NH 2 , CC 6 -Alkoxy, C 1 -C 30 -alkyl or C 6 -C 14 -aryl and the alkyl and aryl fragments of these substituents in turn can be at least monosubstituted with hydroxy, halogen, -CF 3 , -NH 2 or CC 6 -alkoxy, and where that at the carbon atom of the carboxyl group of the general formula (III) directly attached carbon atom of the radical R 3 has no unsubstituted or at least monosubstituted C 6 -C 14 aryl as a substituent.
- R 4 , R 5 and R 6 are, independently of one another, unsubstituted or at least monosubstituted C 1 -C 30 -alkyl, C 6 -C 14 -aryl or C 7 -C 30 -aralkyl, the substituents being selected from hydroxy, halogen, carboxyl, -CF 3 , -NH 2 , CC 6 -alkoxy, CC 30 -alkyl or C 6 -C 14 -aryl and the alkyl and aryl fragments of these substituents in turn with hydroxy, halogen, -CF 3 , -NH 2 or CC 6 -alkoxy at least may be monosubstituted, and where at least one of the radicals R 4 , R 5 or R 6 is unsubstituted or at least monosubstituted C 6 -C 14 aryl,
- R 7 is unsubstituted or at least monosubstituted C 1 -C 4 -alkyl, C 6 -C 14 aryl or C 7 -C 30 aralkyl, wherein the substituents are selected from hydroxy, halogen, carboxyl, -CF 3 , -NH 2 , CC 6 -alkoxy, CrC 30 -alkyl or C 6 -C 14 -aryl and the alkyl and aryl fragments of these substituents in turn with hydroxy, halogen , -CF 3 , -NH 2 or CC 6 -alkoxy can be at least monosubstituted.
- the bismuth-containing catalysts according to the invention are distinguished, inter alia, by the fact that the use of toxic tin-containing catalysts in the production of compounds which contain a urethane group can be avoided.
- the bismuth-containing catalysts according to the invention have a catalyst activity comparable to that of known representatives of the effective, on the one hand catalytically active, but on the other hand toxic tin-containing catalysts.
- the catalyst activity of the bismuth-containing catalysts according to the invention is better than the corresponding catalyst activity of already known bismuth or zinc-containing catalysts.
- the bismuth-containing catalysts according to the invention show an improved hydrolytic stability compared to already known bismuth-containing catalysts. For example, even small amounts of water can be sufficient to significantly or completely reduce the catalyst activity of bismuth-containing catalysts which are based on pure alkyl ligands, such as, for example, laurate-containing bismuth catalysts. While such catalysts known from the prior art begin to precipitate on contact with water, the bismuth-containing catalysts according to the invention are much more stable. Due to the increased hydrolysis stability - and thus also storage stability - the bismut-containing catalysts according to the invention show their improved catalytic properties over a much longer period of time.
- the catalyst must be present as a salt in the corresponding acid.
- the bismuth-containing catalysts according to the invention can therefore also be used without the presence of the corresponding acid in order to form compounds with urethane groups with high catalytic activity.
- the carbonyl carbon is sometimes also counted and designated with position 1. Accordingly, said first carbon atom in direct proximity to the carbon atom of the carboxyl group is sometimes also referred to as the 2 position in chemical nomenclature. Accordingly, according to the invention, there is at least one aromatic substituent, in particular at least one phenyl substituent, on the ⁇ -carbon (atom) or in the 2-position, in the latter case based on the respective total ligand to be considered containing carboxyl groups.
- the said carboxyl group of this substituent is (viewed spatially) in the vicinity of the central bismuth atom of the bismuth-containing catalyst.
- the bismuth-containing catalysts are shown as salts, the bismuth central atom of the bismuth-containing catalyst according to the invention being shown as a (triple positively charged) cation of the corresponding salt (see, for example, the general formula (I)).
- the corresponding substituents / ligands of the bismut-containing catalyst which are represented in the above general formula (I) by the substituents / radicals R 1 , R 2 and X, form the corresponding anion component of the bismut-containing catalyst in this salt representation.
- each of these so-called substituents / ligands is simply negatively charged.
- the two substituents R 1 and R 2 each have a carboxyl group.
- the negative charge in the corresponding substituent / ligand is localized on said carboxyl group and / or the corresponding carboxyl group is in spatial proximity to the (positively charged) bismuth central atom.
- the catalytic activity and / or the hydrolysis stability / storage stability of the bismut-containing catalysts according to the invention is further improved if at least two aromatic substituents, in particular phenyl substituents, are present directly on at least one ligand on the first carbon atom (a-carbon atom / 2-position), which in turn is bonded to the carbon atom of the carboxyl group.
- the alkyl radical can be either linear or branched and, if appropriate, cyclic. Alkyl radicals which have both a cyclic and a linear component also fall under this definition. The same also applies to other alkyl radicals, such as, for example, a CC 6 -alkyl radical or a CrC 12 -alkyl radical.
- alkyl radicals are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, iso-butyl, 2-ethylhexyl, tert-butyl (tert-Bu / t-Bu), pentyl, hexyl, heptyl , Cyclohexyl, octyl, nonyl or decyl.
- aryl or the term “C 6 -C 4 -aryl”, as defined above for the radical R 4 in formula (II), means that the substituent (radical) is an aromatic.
- the corresponding aromatic has a number of carbon atoms from 6 to 14, with any substituents that may be present in the number of carbon atoms not being taken into account.
- the aromatic can be a monocyclic, bicyclic or optionally polycyclic aromatic. In the case of bi- or polycyclic aromatics, individual cycles can optionally be completely or partially saturated. Preferably, all cycles of the corresponding aromatics completely unsaturated.
- Preferred examples of aryl are phenyl, naphthyl or anthracyl, in particular phenyl.
- C 7 -C 3 o-aralkyl as defined for example above for the radical R 4 in formula (II), means that the substituent (radical) is an alkyl radical (such as, for example, CC 6 -alkyl according to the definitions above), this alkyl radical in turn being substituted by an aryl radical (according to the definitions above).
- the corresponding aralkyl substituent has a number of carbon atoms from 7 to 30, with any substituents present not being taken into account in the number of carbon atoms.
- the alkyl radical itself contained therein can be either linear or branched and, if appropriate, cyclic.
- C 1 -C 6 alkoxy as defined above, for example, as an (additional) substituent of the radical R 4 in formula (II), means that this is a substituent (radical) that is derived from an alcohol is derived.
- the corresponding substituent thus contains an oxygen fragment (-0-), which in turn is linked to an alkyl radical, such as CC 6 -alkyl (according to the above definitions).
- the alkyl radical itself can be either linear or branched and, if appropriate, cyclic.
- halogen as defined above for the radical X in formula (I), for example, means that the substituent (radical) is fluorine, chlorine, bromine or iodine; X is preferably fluorine or chlorine, particularly preferred Chlorine.
- the term "unsubstituted or at least monosubstituted C 1 -C 30 alkyl, C 6 -C 14 aryl or C 7 -C 30 aralkyl” means, for example, as defined above for the radical R 4 in formula (II), that each of the three listed substituents (radicals) can either be present in unsubstituted form in accordance with their definitions already mentioned above or at least has one further substituent (monosubstituted). If one or more substituents (for example bisubstituted, trisubstituted or even more highly substituted) are present, the corresponding substituents are selected independently of one another from the substituent groups specified in each case.
- the corresponding aryl building block such as, for example, phenyl
- the corresponding aryl building block can be substituted, for example, with a hydroxy and a CC 30 -alkyl substituent, such as methyl or ethyl.
- Alkyl or aryl fragments can in turn themselves have at least one additional substituent included according to the definitions given. The substitution can take place at any point on the corresponding fragment.
- a corresponding radical such as R 4
- the individual radicals R 4 can be selected completely independently of one another according to the respective definitions.
- the variable x 3 in general formula (I)
- the radical R 1 occurs a total of three times in general formula (I).
- the radical R 1 which in turn comprises the radical R 4 , can thus be present three times independently of one another in this case constellation.
- the individual radicals R 1 can thus be designed differently according to their basic definition. It is thus conceivable that a first radical R 1 has a different definition than the corresponding second and / or third radical R 1 with regard to the constituent of the radical R 4 that is mandatory in it. Unless otherwise stated in the following text, this also applies mutatis mutandis to all other radicals, such as R 2 , R 3 , R 5 and / or R 6 .
- the present invention is further specified below.
- a first object of the present invention is a bismuth-containing catalyst of the general formula (I) in which the variables are defined as follows:
- R 1 is independently a radical of the general formula (II)
- R 2 is independently a radical of the general formula (III)
- X is independently hydroxy, halogen, carbonate, hydrogen carbonate or R 7 and z is 0, 1 or 2; where the sum of x, y and z is 3;
- R 3 is unsubstituted or at least monosubstituted Ci-C 30 alkyl, C 6 -C 14 aryl or C 7 -C 30 aralkyl, the substituents being selected from hydroxy, halogen, carboxyl, -CF 3 , -NH 2 , CC 6 alkoxy, CrC 30 alkyl or C 6 -C 14 aryl and the alkyl and aryl fragments of these substituents can in turn be at least monosubstituted with hydroxy, halogen, -CF 3 , -NH 2 or CC 6 alkoxy, and where the carbon atom of the radical R 3 bonded directly to the carbon atom of the carboxyl group of the general formula (III) has no unsubstituted or at least monosubstituted C 6 -C 14 aryl as a substituent.
- R 4 , R 5 and R 6 are, independently of one another, unsubstituted or at least monosubstituted C 1 -C 30 -alkyl, C 6 -C 14 -aryl or C 7 -C 30 -aralkyl, the substituents being selected from hydroxy, halogen, carboxyl, -CF 3 , -NH 2 , CC 6 -alkoxy, CC 30 -alkyl or C 6 -Ci 4 -aryl and the alkyl and aryl fragments of these substituents in turn with hydroxy, halogen, -CF 3 , -NH 2 or CC 6 -alkoxy at least may be monosubstituted, and where at least one of the radicals R 4 , R 5 or R 6 is unsubstituted or at least monosubstituted C 6 -Ci 4 aryl, R 7 is unsubstituted or at least monosubstituted Ci-C 30 alkyl, C
- a radical R 3 is present which is defined such that the radical R 3 is on the carbon atom which is directly connected to the carbon atom of the corresponding carboxyl group of the general formula (III) is bonded, no unsubstituted or at least monosubstituted C 6 -C 14 aryl, in particular no phenyl, can be present as a direct substituent.
- a substituent is mandatory for at least one of the radicals R 4 , R 5 or R 6 in connection with the radical R 1 according to the general formula (II). Accordingly, it is excluded that a substituent falling under the definition of the radical R 2 according to general formula (III) can simultaneously fall under the corresponding definition of the radical R 1 according to general formula (II).
- the radical R 1 according to general formula (II) is preferably defined according to the invention such that R 4 , R 5 and R 6 are independently unsubstituted or at least monosubstituted C Ci 2 -alkyl or C 6 -Ci 4 -aryl, the substituents being selected are made up of hydroxy, chlorine, -CF 3 and CrC 6 -alkyl, and where at least one of the radicals R 4 , R 5 or R 6 is unsubstituted or at least monosubstituted C 6 -C 14 aryl.
- C 6 -C 14 aryl is preferably phenyl, in particular unsubstituted phenyl.
- R 4 to R 6 in general formula (II) are defined as follows: i) R 4 is unsubstituted or at least monosubstituted phenyl, the substituents being selected from hydroxy, chlorine, -CF 3 and CC 6 -alkyl, ii) R 5 being unsubstituted or at least monosubstituted phenyl or C Ci2-alkyl, the substituents being selected are selected from hydroxy, chlorine, -CF 3 and Ci-C 6 -alkyl, and iii) R 6 is unsubstituted or at least monosubstituted phenyl or C Ci2-alkyl, the substituents being selected from hydroxy, chlorine, -CF 3 and Ci- C 6 alkyl.
- radical R 3 contained therein is unsubstituted or at least monosubstituted CC 12 -alkyl, the substituents being selected from hydroxy, chlorine or -CF 3 .
- radical X it is preferred according to the invention that this is hydroxy, chlorine or R 7 and R 7 is unsubstituted or at least monosubstituted CC 12 -alkyl or C 6 -C 14 -aryl, the substituents being selected from hydroxy, chlorine, - CF 3 and Ci-C 6 alkyl.
- the radicals R 1 , R 2 and X present in each case can each be present in any combination.
- a prerequisite, however, is that x is at least 1, that is to say at least one radical R 1 is present in the bismut-containing catalyst according to the invention according to general formula (I).
- the sum of x, y and z is equal to 3, the total number of ligands or negative charges is 3, so that overall there is charge neutrality with regard to the triple positively charged bismuth central atom. If individual ligands / radicals such as R 1 , R 2 or X occur more than once, they can have the same or different definitions according to the respective basic definition.
- the following case constellations are preferred according to the invention, where i) x is 2 or 3, y is 0 or 1 and z is 0 or 1, or ii) x is 3 and y is and z are each 0, or iii) x is 2, y is 0 and z is 1, or iv) x is 2, y is 1 and z is 0, where x is preferably 3 and y and z are each 0.
- the bismut-containing catalyst according to the general formula (I) and (II) is defined as follows: i) R 4 is unsubstituted or at least monosubstituted phenyl, the substituents being selected from hydroxy, chlorine, -CF 3 and CC 6 alkyl, ii) R 5 is unsubstituted or at least monosubstituted phenyl or C Ci 2 alkyl, the substituents being selected from hydroxy, chlorine, -CF 3 and Ci-C 6 alkyl, iii) R 6 unsubstituted or is at least monosubstituted Ci-Ci 2 -alkyl, the substituents being selected from hydroxy, chlorine and -CF 3 , and iv) x is 3 and y and z are each 0.
- the bismut-containing catalyst is defined as follows: i) R 4 and R 5 are each phenyl, ii) R 6 Ci-Ci 2 -alkyl, preferably C 6 -C 10 -alkyl, in particular C 8 -Alkyl, and iii) x is 3 and y and z are each 0.
- the bismut-containing catalyst is defined by the general formula (Ia):
- the catalyst according to the invention in this embodiment has a total of three radicals R 1 according to general formula (I).
- Each of these three radicals R 1 each contains one radical R 4 , one radical R 5 and one radical R 6 .
- the corresponding definition of the radicals R 4 to R 6 can be identical to or different from one another. According to the invention, however, it is preferred that each of the total of three radicals R 4 is the same, each of the total of three radicals R 5 is the same and each of the total of three radicals R 6 is the same.
- R 4 is unsubstituted or at least monosubstituted phenyl, the substituents being selected from hydroxy, chlorine, -CF 3 and CC 6 -alkyl
- R 5 unsubstituted or at least monosubstituted phenyl or C Ci 2 -alkyl, where the substituents are selected from hydroxy, chlorine, -CF 3 and Ci-C 6 -alkyl
- R 6 is unsubstituted or at least monosubstituted Ci-Ci 2 -alkyl, where the substituents are selected from hydroxy, chlorine and -CF 3 .
- R 4 and R 5 are each phenyl, and ii) R 6 Ci-Ci 2 -alkyl, preferably C 6 -C 10 -alkyl, in particular C 8 -Alkyl is.
- the present invention thus also provides a process for the preparation of a bismut-containing catalyst of the general formula (I) or of the general formula (Ia) as defined above.
- any bismuth-containing compound can be used in the process according to the invention which is suitable for forming the central bismuth atom in the bismuth-containing catalyst according to the invention according to the general formula (I) by reaction with the corresponding compounds according to the general formula (IIa) or optionally (purple) .
- Bismuth-containing bonds as such are known to the person skilled in the art.
- a bismuth halide is used as the bismuth-containing compound, it is preferably a chlorine-containing compound, in particular BiCl 3 .
- any special substituents / substitution patterns for example on the radicals R 4 to R 6 , can, according to the invention, already be present in the corresponding starting material. If appropriate, such substituents / substitution patterns can also be attached or completed only after the production process described above for a bismuth-containing catalyst according to the general formula (I).
- the bismuth-containing compound is preferably selected from Bi 2 O 3 , BiCl 3 , Bi (C 6 H 5 ) 3 or metallic bismuth.
- the bismuth-containing catalysts according to the invention according to the general formula (I) are preferably prepared by reacting at least one compound of the general formula (IIIa) and optionally at least one compound of the general formula (IIIa) with at least one bismuth-containing compound, i) the reaction under a protective atmosphere and / or in the presence of at least one solvent, in particular toluene or tetrahydrofuran, and / or ii) the reaction is carried out for at least 10 hours and / or at a temperature of at least 100 ° C., and / or iii) subsequently volatile constituents are removed after the reaction, the bismut-containing catalyst is dried in vacuo and / or recrystallization is carried out.
- the at least one compound of the general formula (IIIa) used as starting material in the process according to the invention is prepared from a corresponding compound according to the general formula (Mb), the compounds according to the general formula (IIIa) from differentiate the corresponding compounds of the general formula (IIb) only in that one or a maximum of two radicals selected from R 4 , R 5 and R 6 are defined as H (hydrogen) instead of the definitions given for the compounds according to general formula (IIIa).
- This process variant is used in particular when a catalyst according to the invention is to be prepared according to the general formula (I) in which at least one of the radicals R 4 to R 6 , preferably exactly one of these radicals, is a C 1 -C 30 alkyl.
- a corresponding halo-aryl or halo-aralkyl compound is used instead of a haloalkane, provided that a fully or partially aromatic substituent is to be introduced into the corresponding compound (Mb) in this process step.
- the compound according to the general formula (Mb) is preferably 2-arylacetic acid, 2,2-diarylacetic acid, in particular 2-phenylacetic acid or 2,2-diphenylacetic acid, particularly preferably 2,2-diphenylacetic acid.
- Another object of the present invention is the use of at least one bismuth-containing catalyst as defined above for the preparation of compounds which contain a urethane group.
- reaction solution is mixed with a saturated ammonium chloride solution (60 mL) and stirred for 30 minutes.
- the aqueous phase is separated off using a separating funnel and extracted in each case with 3 ⁇ 25 mL diethyl ether.
- the collected organic phases are dried over magnesium sulfate (MgS0 4 ).
- MgS0 4 magnesium sulfate
- Triphenyl bismuth (1.1 g; 2.5 mmol) and 2,2-diphenyldecanoic acid (2.43 g; 7.5 mmol) are placed in a 25 mL three-necked flask with a stir bar, reflux condenser, thermometer and protective gas inlet (argon or nitrogen) under a protective gas atmosphere submitted.
- the starting materials are mixed with 12.5 mL dry tetrahydrofuran or dry toluene (5 mL solvent per 1 mmol triphenyl bismuth) and heated at 110 ° C. for at least 16 hours under a protective gas atmosphere.
- the progress of the reaction is monitored by means of 1 H-NMR (nuclear magnetic resonance spectroscopy).
- the catalyst Bi (dpp) 3 according to Example 4 is prepared analogously to the above-described catalyst Bi (dpd) 3 , whereby no synthesis of the precursor is required because the corresponding propionic acid derivative is commercially available (from Sigma-Aldrich), which with triphenyl bismuth to the invention Catalyst Bi (dpp) 3 is implemented.
- II) Determination of the catalyst activity for Examples 1 to 5 The following table 1 shows the respective catalyst activity of the individual exemplary and comparative examples. The activity of the catalyst is checked by a reaction in which a compound containing a urethane group is formed.
- the isocyanate decrease and thus the formation of a urethane group are investigated by means of horizontal ATR-IR spectroscopy.
- 0.05 mL are removed from the reaction solution at defined time intervals and spectroscoped directly.
- the conversion is determined on the basis of the relative decrease in intensity of the asymmetrical isocyanate stretching oscillation at 2250-2285 cm 1 .
- the starting content of free isocyanate was determined at room temperature of the reaction solution in the absence of a catalyst. All IR spectra were normalized to the bands of the symmetrical and asymmetrical stretching vibrations of the CH 2 groups (3000-2870 cm- 1 ).
- the individual catalysts used in Table 1 are:
- the two inventive catalysts according to embodiment 1 and embodiment 4 show a comparable catalytic activity to the known tin-containing catalysts according to comparative example 2.
- tin-containing catalysts are to be avoided due to their considerable toxicity.
- the catalytic activity of Examples 1 and 4 is significantly improved compared to bismuth-containing catalysts according to the prior art (Comparative Example 3) or when the experiment was carried out entirely without a catalyst (Comparative Example 5).
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Abstract
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---|---|---|---|---|
GB1258357A (de) * | 1970-04-23 | 1971-12-30 | ||
LU81024A1 (fr) * | 1979-03-09 | 1980-09-24 | Prb Sa | Procede pour la preparation de polyurethanne a peau integrale et polyurethanne obtenu |
JPS5887087A (ja) | 1981-11-18 | 1983-05-24 | Oji Paper Co Ltd | 記録用呈色シ−ト |
US4895827A (en) | 1987-12-04 | 1990-01-23 | Appleton Papers Inc. | Thermally-responsive record material |
JP3097774B2 (ja) * | 1991-11-05 | 2000-10-10 | ダイセル化学工業株式会社 | ポリカーボネートの製造法 |
US6353057B1 (en) * | 1999-02-10 | 2002-03-05 | King Industries, Inc. | Catalyzing cationic resin and blocked polyisocyanate with bismuth carboxylate |
BRPI0818584B1 (pt) * | 2007-10-17 | 2019-05-28 | Basf Se | Uso de um composto catalisador latente, composição polimerizável, processo para polimerização de compostos, uso da composição polimerizável, substrato revestido, composição polimerizada ou reticulada, e, composto catalisador latente |
EP2604615A1 (de) * | 2011-12-12 | 2013-06-19 | Sika Technology AG | Bismuthaltiger Katalysator für Polyurethan-Zusammensetzungen |
CA3038858A1 (en) | 2016-10-13 | 2018-04-19 | Basf Coatings Gmbh | Coating material system based on salts of an aliphatic monocarboxylic acid |
-
2020
- 2020-01-24 EP EP20701200.6A patent/EP3921352A1/de not_active Withdrawn
- 2020-01-24 US US17/427,761 patent/US20220118431A1/en active Pending
- 2020-01-24 WO PCT/EP2020/051793 patent/WO2020160939A1/de unknown
- 2020-01-24 CN CN202080012083.XA patent/CN113383026A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
CN113383026A (zh) | 2021-09-10 |
US20220118431A1 (en) | 2022-04-21 |
WO2020160939A1 (de) | 2020-08-13 |
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