EP1404444A2 - Method for the production of cycloaliphatic compounds (1) having side chains with epoxy groups - Google Patents
Method for the production of cycloaliphatic compounds (1) having side chains with epoxy groupsInfo
- Publication number
- EP1404444A2 EP1404444A2 EP02758224A EP02758224A EP1404444A2 EP 1404444 A2 EP1404444 A2 EP 1404444A2 EP 02758224 A EP02758224 A EP 02758224A EP 02758224 A EP02758224 A EP 02758224A EP 1404444 A2 EP1404444 A2 EP 1404444A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- ruthenium
- catalyst
- hydrogenation
- compound
- weight
- 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.)
- Ceased
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 125000003700 epoxy group Chemical group 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 94
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 54
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000012876 carrier material Substances 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 8
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims abstract description 7
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 5
- 125000002837 carbocyclic group Chemical group 0.000 claims abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 11
- -1 aromatic glycidyl ethers Chemical class 0.000 claims description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 2
- 229940117900 2,2-bis(4-glycidyloxyphenyl)propane Drugs 0.000 claims 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000002243 precursor Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XWURZHGKODQZMK-UHFFFAOYSA-N O.[Ru]=O Chemical compound O.[Ru]=O XWURZHGKODQZMK-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000000466 oxiranyl group Chemical group 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010414 supernatant solution Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- WOSOOWIGVAKGOC-UHFFFAOYSA-N azanylidyneoxidanium;ruthenium(2+);trinitrate Chemical compound [Ru+2].[O+]#N.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WOSOOWIGVAKGOC-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NIOYEYDJTAEDFH-UHFFFAOYSA-N 1-(2-hydroxyethoxy)-2-methylpropan-2-ol Chemical compound CC(C)(O)COCCO NIOYEYDJTAEDFH-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- AQKZSTFCPAOFIV-UHFFFAOYSA-N 2-[(4-ethylphenoxy)methyl]oxirane Chemical compound C1=CC(CC)=CC=C1OCC1OC1 AQKZSTFCPAOFIV-UHFFFAOYSA-N 0.000 description 1
- IGZBSJAMZHNHKE-UHFFFAOYSA-N 2-[[4-[bis[4-(oxiran-2-ylmethoxy)phenyl]methyl]phenoxy]methyl]oxirane Chemical class C1OC1COC(C=C1)=CC=C1C(C=1C=CC(OCC2OC2)=CC=1)C(C=C1)=CC=C1OCC1CO1 IGZBSJAMZHNHKE-UHFFFAOYSA-N 0.000 description 1
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 description 1
- XORPRFYPJCYNOQ-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline;methanediamine Chemical compound NCN.C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 XORPRFYPJCYNOQ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- GXVFTWIOEXXVPU-UHFFFAOYSA-N C1OC1COC1=CC=CC=C1C(CC12)CC1C(C1)CC2C1C1=CC=CC=C1OCC1CO1 Chemical compound C1OC1COC1=CC=CC=C1C(CC12)CC1C(C1)CC2C1C1=CC=CC=C1OCC1CO1 GXVFTWIOEXXVPU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical class C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000012905 visible particle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
- C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
Definitions
- the invention relates to a process for the preparation of cycloaliphatic compounds I which have side chains with epoxy groups by heterogeneously catalytic hydrogenation of a compound II which has at least one carbocyclic, aromatic group and at least one side chain with at least one epoxy group on one ruthenium catalyst.
- cycloaliphatic oxirane compounds I which have no aromatic groups is of particular interest for the production of light and weather-resistant coating systems.
- such compounds can be prepared by hydrogenating aromatic compounds II with side chains containing oxirane groups, such as glycidyl groups.
- the compounds I are therefore also referred to as "core-hydrogenated” oxirane compounds.
- the compounds II have long been known as constituents of coating systems (see J.W. Muskopf et al. "Epoxy Resins" in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM).
- US Pat. No. 3,336,241 teaches the hydrogenation of aromatic epoxy compounds using rhodium and ruthenium catalysts for the preparation of cycloaliphatic compounds with epoxy groups.
- the activity of the catalysts decreases so much after a hydrogenation that in an industrial process the catalyst has to be changed after each hydrogenation.
- the selectivity of the catalysts described there leaves something to be desired.
- DE-A 36 29 632 and DE-A 39 19 228 teach the selective hydrogenation of the aromatic molecular parts of bis [glycidyloxiphenyljmethane (bisphenol F) or of 2,2-bis [p-glycidyloxiphenyl] propane (bisphenol A) on ruthenium oxide hydrate. This improves the selectivity of the hydrogenation with regard to the aromatic groups to be hydrogenated. According to this teaching, however, it is advisable to regenerate the catalyst after each hydrogenation, the separation of the catalyst from the reaction mixture proving to be problematic.
- EP-A 678512 teaches the selective hydrogenation of the aromatic molecular parts of aromatic compounds with oxirane groups on ruthenium catalysts, preferably ruthenium oxide hydrate, in the presence of 0.2 to 10% by weight of water, based on the reaction mixture.
- ruthenium catalysts preferably ruthenium oxide hydrate
- step ii) is carried out immediately after step i).
- the present invention relates to a process for the preparation of cycloaliphatic compounds I which have side chains with epoxy groups by heterogeneously catalytic hydrogenation of a compound II which has at least one carbocyclic, aromatic group and at least one side chain with at least one epoxy group on one Ruthenium catalyst, which is characterized in that a ruthenium catalyst defined above is used as the catalyst.
- the process according to the invention is distinguished by high activities and high selectivities of the catalysts used with regard to the hydrogenation of the aromatic parts of the molecule in the compounds II.
- the activities are clearly above the activities which are achieved in the methods of the prior art, with comparable or improved selectivity. Because of this, high space-time yields can be achieved even under comparatively mild reaction conditions.
- the catalysts used in the process according to the invention are distinguished by long service lives.
- the high activity of the catalysts used in the process according to the invention can be attributed to the particularly good distribution of the ruthenium on the surface of the support material and to the substantial absence of halogen in the support material.
- the ruthenium is present in the catalysts according to the invention as metallic ruthenium.
- Electron microscopic investigations (TEM) of the catalysts have shown that the ruthenium on the support material is in atomic-dipseric form and / or in the form of ruthenium particles which are almost exclusively, ie more than 90%, preferably more than 95%, based on the number of visible particles, as isolated particles with diameters below 10 nm, in particular below 7 nm.
- the catalyst contains essentially none, ie less than 10%, in particular less than 5%, of ruthenium particles and / or agglomerates of ruthenium particles with diameters above 10 nm.
- the chlorine content of the catalysts used according to the invention is also below 0.05% by weight ( ⁇ 500 ppm), based on the total weight of the Catalyst.
- all ppm figures are to be understood as parts by weight, unless stated otherwise.
- An essential component of the catalysts used in the process according to the invention is the support material based on amorphous silicon dioxide.
- amorphous means that the proportion of crystalline silicon dioxide phases makes up less than 10% of the carrier material.
- the support materials used to manufacture the catalysts can, however, have superstructures which are formed by regular arrangement of pores in the support material.
- amorphous silicon dioxide types which consist of at least 90% by weight of silicon dioxide come into consideration as carrier materials, the remaining 10% by weight, preferably not more than 5% by weight of the carrier material also being of another oxidic type Material can be, for example MgO, CaO, Ti0 2 , Zr0 2 , Fe 2 Ü 3 or alkali metal oxide.
- the carrier material used is also halogen-free, ie the halogen content is less than 500 ppm.
- the carrier material preferably contains no more than 1% by weight and in particular no more than 0.5% by weight and in particular no detectable amounts ( ⁇ 500 ppm) of aluminum oxide, calculated as Al 2 O 3 .
- support materials are used which contain less than 500 ppm Fe 2 0 3 .
- the proportion of alkali metal oxide generally results from the production of the carrier material and can be up to 2% by weight. It is often less than 1% by weight.
- Alkali metal oxide-free carriers ( ⁇ 0.1% by weight) are also suitable.
- the proportion of MgO, CaO, Ti0 2 or Zr0 2 can make up to 10% by weight of the carrier material and is preferably not more than 5% by weight.
- carrier materials which do not contain any detectable amounts of these metal oxides are also suitable.
- the carrier material is halogen-free, ie the halogen content in the carrier material is less than 500 ppm.
- Support materials are preferred which have a specific surface area in the range from 30 to 700 m 2 / g, preferably 30 to 300 m 2 / g (BET surface area in accordance with DIN 66131).
- Suitable amorphous support materials based on silicon dioxide are familiar to the skilled worker and are commercially available (see, for example, OW Flörke, "Silica” in Ullmann's Encyclopedia of Industrial Chemistry 5th ed. On CD-ROM). They can have been made both naturally and artificially.
- suitable amorphous carrier materials based on silicon dioxide are diatomaceous earth, silica gels, pyrogenic silica and precipitated silica seiklare.
- the catalysts have silica gels as support materials.
- the carrier material can have different shapes.
- the support material in the form of a finely divided powder will usually be used to produce the catalysts according to the invention.
- the powder preferably has particle sizes in the range from 1 to 200 ⁇ m, in particular 1 to 100 ⁇ m.
- moldings made from the support material are usually used, e.g. are available by extrusion, extrusion or tabletting and which e.g. can have the shape of balls, tablets, cylinders, strands, rings or hollow cylinders, stars and the like.
- the dimensions of these moldings usually range from 1 mm to 25 mm. Catalyst strands with strand diameters of 2 to 5 mm and strand lengths of 2 to 25 mm are often used.
- the content of ruthenium in the catalysts can be varied over a wide range. As a rule, it will be at least 0.1% by weight, preferably at least 0.2% by weight, and often will not exceed a value of 10% by weight, in each case based on the weight of the carrier material and calculated as elemental ruthenium ,
- the ruthenium content is preferably in the range from 0.2 to 7% by weight and in particular in the range from 0.4 to 5% by weight.
- the ruthenium catalysts used in the process according to the invention are generally prepared by first treating the support material with a halogen-free aqueous solution of a low molecular weight ruthenium compound, hereinafter referred to as (ruthenium precursor), in such a way that the desired amount of ruthenium from the support material This step is also referred to below as impregnation, and the carrier treated in this way is then dried in compliance with the temperature limits specified above, and the solid obtained is then treated again with the aqueous solution of the ruthenium precursor and dried again often repeated until the amount of ruthenium compound taken up by the support material corresponds to the desired ruthenium content in the catalyst.
- ruthenium precursor a halogen-free aqueous solution of a low molecular weight ruthenium compound
- the treatment or impregnation of the carrier material can take place in different ways and depends in a known manner on the shape of the carrier material. For example, you can Spray or rinse the carrier material with the precursor solution or suspend the carrier material in the precursor solution.
- the carrier material can be suspended in the aqueous solution of the ruthenium precursor and filtered off from the aqueous supernatant after a certain time.
- the ruthenium content of the catalyst can then be controlled in a simple manner via the amount of liquid taken up and the ruthenium concentration of the solution.
- the support material can also be impregnated, for example, by treating the support with a defined amount of the aqueous solution of the ruthenium precursor that corresponds to the maximum amount of liquid that the support material can hold.
- the carrier material can be sprayed with the required amount of liquid.
- Suitable apparatus for this are the apparatus usually used for mixing liquids with solids (see Vauck / Müller, Basic Operations of Chemical Process Engineering, 10th edition, German Publishing House for Basic Industry, 1994, p. 405 ff.), For example tumble dryers, water drums, drum mixers, paddle mixers and like.
- Monolithic supports are usually rinsed with the aqueous solutions of the ruthenium precursor.
- the aqueous solutions used for impregnation are preferably halogen-free, ie they contain no or less than 500 ppm halogen, in particular less than 100 ppm halogen, based on the total weight of the solution. Therefore, only ruthenium compounds that do not contain chemically bound halogen and that are sufficiently soluble in the aqueous solvent are used as ruthenium precursors. These include, for example, ruthenium (III) nitrosyl nitrate (Ru (NO) (N0 3 ) 3 ), ruthenium (III) acetate and the alkali metal ruthenates (IV) such as sodium and potassium ruthenate (IV). In principle, however, halogen-containing ruthenium precursors such as RuCl 3 or mixtures thereof with halogen-free ruthenium precursors can also be used.
- aqueous here denotes water and mixtures of water with up to 50% by volume, preferably not more than 30% by volume and in particular not more than 10% by volume, of one or more water-miscible organic solvents, for example Mixtures of water with -CC alkanols such as methanol, ethanol, n- or isopropanol. Water is often used as the sole solvent.
- the aqueous solvent will often additionally contain at least one halogen-free acid, for example nitric acid, sulfuric acid, phosphoric acid or acetic acid, preferably a halogen-free mineral acid, in order to stabilize the ruthenium precursor in the solution. In many cases, therefore, a halogen-free mineral acid, e.g. B.
- the concentration of the ruthenium precursor in the aqueous solutions naturally depends on the amount of ruthenium precursor to be applied and the absorption capacity of the support material for the aqueous solution and is generally in the range from 0.1 to 20% by weight.
- Drying can be carried out in accordance with the customary methods of drying solids while observing the above-mentioned upper temperature limits. Compliance with the upper limit of the invention
- Drying temperatures is for quality, i.e. the activity of the catalyst is important. Exceeding the drying temperatures given above leads to a significant loss of activity. Calcining the carrier at higher temperatures, e.g. Above 300 ° C. or even 400 ° C., as is proposed in the prior art, is not only superfluous but also has a disadvantageous effect on the activity of the catalyst. To submit sufficient drying speeds, drying is usually carried out at an elevated temperature, e.g. B. at at least 40 ° C, in particular at least 70 ° C and especially at least 100 ° C.
- an elevated temperature e.g. B. at at least 40 ° C, in particular at least 70 ° C and especially at least 100 ° C.
- the drying of the solid impregnated with the ruthenium precursor usually takes place under normal pressure, and a reduced pressure can also be used to promote the drying. Often, to promote drying, a gas flow will be passed over or through the material to be dried, e.g. Air or nitrogen.
- the drying time naturally depends on the desired degree of drying and the drying temperature and is generally in the range from 2 h to 30 h, preferably in the range from 4 to 15 h.
- the treated carrier material is preferably dried to such an extent that the content of water or volatile solvent components before the reduction ii) is less than 5% by weight, in particular not more than 2% by weight and particularly preferably not more than 1% by weight .-%, based on the total weight of the solid.
- the weight percentages here relate to the weight loss of the solid, determined at a temperature of 300 ° C., a pressure of 1 bar and a duration of 10 min. In this way, the activity of the catalysts used according to the invention can be increased further. Drying is preferably carried out by moving the solid treated with the precursor solution, for example by drying the solid in a rotary tube oven or a rotary ball oven. In this way, the activity of the catalysts according to the invention can be increased further.
- the solid obtained after drying is converted into its catalytically active form by hydrogenating the solid at the temperatures indicated above in a manner known per se (step ii)).
- the carrier material is brought into contact with hydrogen or a mixture of hydrogen and an inert gas at the temperatures indicated above.
- the hydrogen partial pressure is of minor importance for the result of the reduction and will generally be varied in the range from 0.2 bar to 1.5 bar.
- the hydrogenation of the catalyst material often takes place at normal hydrogen pressure in a hydrogen stream.
- the hydrogenation is preferably carried out by moving the solid obtained in i), for example by hydrogenating the solid in a rotary tubular furnace or a rotary ball furnace. In this way, the activity of the catalysts according to the invention can be increased further.
- the catalyst can be passivated in a known manner to improve handling, e.g. by briefly mixing the catalyst with an oxygen-containing gas, e.g. Air, but preferably treated with an inert gas mixture containing 1 to 10% by volume of oxygen.
- an oxygen-containing gas e.g. Air
- an inert gas mixture containing 1 to 10% by volume of oxygen
- Suitable starting compounds II are all organic molecules which carry at least one carbocyclic aromatic group, preferably at least one benzene ring, and at least one side chain with oxirane group.
- the side chains are epoxidized C 3 -C ⁇ o-alkenyl groups, for example glydidyl groups (2, 3-0xypropen-l-yl), which are directly or via a hetero atom, for example via oxygen or nitrogen, or via a Carboxyl or a carboxamide group are attached to the aromatics.
- the compounds II can of course have one or more aromatic groups which are linked to one another via oxygen or nitrogen atoms or via alkylene or cycloalkylene groups. In the compounds II, of course, each of the aromatic groups or a part of the aromatic groups can have side chains with oxirane groups.
- Compounds II can be both monomeric and oligomeric or polymeric compounds.
- Bisphenol A or bisphenol F or comparable compounds can be reacted with epichlorohydrin and bases in a known manner (e.g. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, VCH (1987) Vol. A9, p. 547) to give glycidyl ethers of the general formula Ha,
- R 2 represents hydrogen or a -CC alkyl group, for example methyl, or two radicals R 2 bonded to a carbon atom form a C 3 -C 5 alkylene group and m represents zero to 40.
- Novolaks of the general formula IIb can be obtained by acid-catalyzed reaction of phenol or cresol and conversion of the reaction products to the corresponding glycidyl ethers (see e.g. bis [4- (2,3-epoxypropoxy) phenyl] methane):
- Glycidyl ethers are accessible by acid-catalyzed reaction of phenol and aldehydes and subsequent reaction with epichlorohydrin, e.g. is 1, 1, 2, 2-tetrakis
- Glycidyl ethers of phenol hydrocarbon novolacs e.g. , 2, 5-bis [(glycidyloxy) phenyl] octahydro-4, 7-methano-5H-indene and its oligomers.
- Aromatic glycidylamines :
- Exemplary are the triglycidyl compound of p-aminophenol, 1- (glycidyloxy) -4- [N, N-bis (glycidyl) amino] benzene, and the tetraglycidyl compound of methylenediamine bis ⁇ 4- [N, N- bis (2, 3-epoxypropyl) amino] phenyl ⁇ methane to name.
- Glycidyl esters of aromatic mono-, di- and tricaronic acids e.g. Phthalic acid and isophthalic acid diglycidyl esters.
- Particularly preferred starting compounds are di- [p-glycidoxiphenylj-methane and 2,2-di- [p-glycidoxiphenyl] propane and oligomers of these compounds which still have glycidyl groups.
- the hydrogenation of the compounds II generally takes place in the liquid phase. Because of the partially high viscosity of the compounds II, they will preferably be used as a solution or mixture in an organic solvent. In principle, there are organic solvents into consideration, which are able to dissolve the compound II as completely as possible or mix completely with it and which are inert under the hydrogenation conditions, ie are not hydrogenated.
- Suitable solvents are cyclic and alicyclic ethers, for example tetrahydrofuran, dioxane, methyl tert-butyl ether, dimethoxyethane, dimethoxypropane, dimethyldiethylene glycol, aliphatic alcohols such as methanol, ethanol, n- or isopropanol, n-, 2-, iso- or tert-butanol and aliphatic ether alcohols such as methoxypropanol.
- concentration of compound II in the liquid phase to be hydrogenated can in principle be chosen freely and is frequently in the range from 20 to 95% by weight, based on the total weight of the solution / mixture. In the case of compounds II which are sufficiently free-flowing under the reaction condition, the hydrogenation can also be carried out in the absence of a solvent.
- the proportion of water, based on the mixture to be hydrogenated can be up to 10% by weight, e.g. 0.1 to 10 wt .-%, preferably 0.2 to 7 wt .-% and in particular 0.5 to 5 wt .-%.
- the actual hydrogenation usually takes place in analogy to the known hydrogenation processes for the preparation of compounds I, as described in the prior art mentioned at the outset.
- the compound II preferably as a liquid phase
- the catalyst can be suspended in the liquid phase (suspension mode) or the liquid phase is passed over a fluidized catalyst bed (fluidized bed mode) or a fixed catalyst bed (fixed bed mode).
- the hydrogenation can be carried out either continuously or batchwise.
- the process according to the invention is preferably carried out in trickle reactors according to the fixed bed procedure.
- the hydrogen can be passed both in cocurrent with the solution of the starting material to be hydrogenated and in countercurrent over the catalyst.
- Suitable apparatus for carrying out a hydrogenation according to the suspension procedure as well as for hydrogenation on the catalyst fluidized bed and on the fixed catalyst bed are known from the prior art, for example from Ullmanns Enzyklopadie der Technischen Chemie, 4th edition, volume 13, p. 135 ff. And from PN Rylander, "Hydrogenation and Dehydrogenation” in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed. On CD-ROM.
- the hydrogenation can be carried out both at normal hydrogen pressure and at elevated hydrogen pressure, for example at a hydrogen partial pressure of at least 1.1 bar, preferably at least 10 bar. As a rule, the hydrogen partial pressure will not exceed 325 bar and preferably 300 bar.
- the hydrogen partial pressure is particularly preferably in the range from 50 to 300 bar.
- the reaction temperatures are usually at least 30 ° C and will often not exceed 150 ° C.
- the hydrogenation process is carried out at temperatures in the range from 40 to 100 ° C. and particularly preferably in the range from 50 to 80 ° C.
- reaction gases also include hydrogen-containing gases which do not contain any catalyst poisons such as carbon monoxide or gases containing sulfur, e.g. Mixtures of hydrogen with inert gases such as nitrogen or reformer exhaust gases, which usually still contain volatile hydrocarbons. Pure hydrogen (purity> 99.99% by volume) is preferably used.
- the starting material II to be hydrogenated is usually used in an amount of 0.05 to 3 kg / (1 (catalyst) * h), in particular 0.2 to 2 kg / (1 (catalyst) * h) lead the catalyst.
- the catalysts used in this process can of course be regenerated according to the methods known to those skilled in the art for noble metal catalysts such as ruthenium catalysts.
- a solvent e.g. B. water, rinse.
- the decrease in the epoxy groups was determined by comparing the epoxy equivalent before and after the hydrogenation, determined in each case in accordance with ASTM-D-1652-88.
- a defined amount of carrier material in a bowl was soaked with the maximum amount of a solution of ruthenium (III) nitrosyl nitrate in water that could be absorbed by the respective carrier material.
- the maximum amount of liquid absorbed by the respective carrier material had previously been determined using an authentic sample.
- the concentration of the solution was measured so that the desired concentration of ruthenium in the support material resulted.
- the solid thus obtained was then dried in a rotary ball oven at 120 ° C. for 13 hours and had a residual water content of ⁇ 1% by weight (determined as the weight loss of a sample dried at 300 ° C. and 1 bar for 10 minutes).
- the solid obtained in this way was reduced in a reaction tube at 300 ° C. for 4 h in a hydrogen stream at normal pressure. After cooling and inerting with nitrogen, the catalyst was removed by passing 5% by volume of air in nitrogen over a period of 120 min. passivated.
- Catalyst A carrier material silica gel powder with an SiO 2 content> 99.5% by weight and a specific BET surface area of 68 m 2 / g, a water absorption of 1.12 ml / g and a particle size ⁇ 100 ⁇ m.
- Ruthenium content of catalyst A 4.6% by weight.
- Catalyst B silica gel strands (d 4 mm, 1 1 to 10 mm) with an SiO 2 content> 99.5% by weight (0.3% by weight Na 2 0), a specific BET surface area of 169 m 2 / g, a water absorption of 0.95 ml / g and a pore volume of 0.7 ml / g (DIN 66134).
- Ruthenium content of catalyst B 4.7% by weight
- Comparative catalyst ruthenium oxide hydrate
- Ruthenium oxide hydrate is obtained as a water-moist precipitate by reacting an aqueous solution of ruthenium-III-chloride hydrate, RuCl 3 x 3H 2 0, with sodium hydroxide solution at pH 8 and then washing with water and THF.
- the residual aromatic content was 2.3% after the first hydrogenation, 18.1% after the second hydrogenation and 27% after the third hydrogenation.
- the proportion of hydrogenated epoxy groups was less than 5% in the first run. 2 g Ru / kg diglycidyl ether were required.
- the reactor was an electrically heated reaction tube made of stainless steel, which was filled with 75 g of catalyst B (160 mL), a feed pump for the educt, devices for sampling, and a separator with level control and exhaust gas control.
- the reaction tube was flowed through from bottom to top.
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10128204A DE10128204A1 (en) | 2001-06-11 | 2001-06-11 | Production of cycloaliphatic compounds that have side chains containing epoxy groups, useful for the production of weather resistant paint systems, comprises use of a supported ruthenium catalyst. |
DE10128204 | 2001-06-11 | ||
PCT/EP2002/006348 WO2002100538A2 (en) | 2001-06-11 | 2002-06-10 | Method for the production of cycloaliphatic compounds having side chains with epoxy groups by hydrogenation on ru/s102 catalysts |
Publications (1)
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EP1404444A2 true EP1404444A2 (en) | 2004-04-07 |
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EP02758224A Ceased EP1404444A2 (en) | 2001-06-11 | 2002-06-10 | Method for the production of cycloaliphatic compounds (1) having side chains with epoxy groups |
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US (1) | US20040176549A1 (en) |
EP (1) | EP1404444A2 (en) |
JP (1) | JP2004529200A (en) |
KR (1) | KR20040030664A (en) |
CN (1) | CN1239488C (en) |
AU (1) | AU2002325235A1 (en) |
DE (1) | DE10128204A1 (en) |
WO (1) | WO2002100538A2 (en) |
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US20070112210A1 (en) * | 2003-12-22 | 2007-05-17 | Basf Aktiengesellschaft | Heterogeneous ruthenium catalyst, methods for hydrogenating a carbocyclic aromatic group, and nucleus-hydrogenated diglycidyl ether of bisphenols a and f |
DE10361157A1 (en) * | 2003-12-22 | 2005-07-21 | Basf Ag | Heterogeneous ruthenium catalyst, useful for hydrogenating bis-glycidyloxyphenyl-alkanes to cyclohexane analogs, for use in lacquers, has silica carrier with specific nuclear magnetic resonance characteristics |
DE102005027567A1 (en) | 2005-06-14 | 2006-12-21 | Basf Ag | Process for passivating metallic surfaces with polymers having acid groups |
DE102005029200A1 (en) | 2005-06-22 | 2006-12-28 | Basf Ag | Shell catalyst, useful e.g. for hydrogenating organic compound, comprises ruthenium alone or in combination with a transition metal, applied to a carrier containing silicon dioxide |
WO2006136569A1 (en) * | 2005-06-22 | 2006-12-28 | Basf Aktiengesellschaft | Heterogeneous ruthenium catalyst and method for hydrogenating a carboxylic aromatic group, in particular for producing core hydrogenated bisglycidyl ether bisphenols a and f |
EP1921057B1 (en) * | 2005-08-26 | 2012-01-25 | Asahi Kasei Chemicals Corporation | Process for production of cycloolefin |
DE102005062354A1 (en) * | 2005-12-23 | 2007-06-28 | Basf Ag | Conversion of an aromatic hydrocarbon containing sulfur containing aromatic compounds comprises lowering the content of the sulfur containing compound, and hydrogenating the aromatic hydrocarbon |
JP5759381B2 (en) | 2008-12-17 | 2015-08-05 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Continuous process for the production of substituted cyclohexylmethanols |
EP2512658A2 (en) * | 2009-12-15 | 2012-10-24 | Basf Se | Catalyst and method for hydrogenating aromates |
WO2015138128A1 (en) | 2014-03-12 | 2015-09-17 | Dow Global Technologies Llc | Epoxy resin compositions |
US10150102B2 (en) * | 2014-03-12 | 2018-12-11 | Dow Global Technologies Llc | Catalyst regeneration process |
CN114570361B (en) * | 2022-03-30 | 2023-01-06 | 福州大学 | Ru-based catalyst for ammonia decomposition hydrogen production and preparation method thereof |
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US3336241A (en) * | 1963-11-12 | 1967-08-15 | Shell Oil Co | Process for preparing epoxy compounds and resulting products |
DE3629632A1 (en) * | 1986-08-30 | 1988-03-03 | Basf Ag | METHOD FOR PRODUCING 2,2-DI- (P-GLYCIDOXI-CYCLOHEXYL) PROPANE |
JP2814711B2 (en) * | 1990-07-13 | 1998-10-27 | 三菱化学株式会社 | Method for producing cycloolefin |
US5334790A (en) * | 1992-02-26 | 1994-08-02 | Catalytica | Process and catalyst for partially hydrogenating aromatics to produce cycloolefins |
DE4414089A1 (en) * | 1994-04-22 | 1995-10-26 | Basf Ag | Process for the selective hydrogenation of aromatic groups in the presence of epoxy groups |
US6130344A (en) * | 1997-11-27 | 2000-10-10 | Mitsubishi Chemical Corporation | Process for producing compound having epoxy group |
-
2001
- 2001-06-11 DE DE10128204A patent/DE10128204A1/en not_active Withdrawn
-
2002
- 2002-06-10 WO PCT/EP2002/006348 patent/WO2002100538A2/en not_active Application Discontinuation
- 2002-06-10 EP EP02758224A patent/EP1404444A2/en not_active Ceased
- 2002-06-10 CN CNB028132777A patent/CN1239488C/en not_active Expired - Fee Related
- 2002-06-10 US US10/480,239 patent/US20040176549A1/en not_active Abandoned
- 2002-06-10 KR KR20037016145A patent/KR20040030664A/en not_active Application Discontinuation
- 2002-06-10 AU AU2002325235A patent/AU2002325235A1/en not_active Abandoned
- 2002-06-10 JP JP2003503350A patent/JP2004529200A/en not_active Withdrawn
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AU2002325235A1 (en) | 2002-12-23 |
KR20040030664A (en) | 2004-04-09 |
CN1239488C (en) | 2006-02-01 |
CN1535175A (en) | 2004-10-06 |
AU2002325235A8 (en) | 2005-10-13 |
DE10128204A1 (en) | 2002-12-12 |
JP2004529200A (en) | 2004-09-24 |
WO2002100538A2 (en) | 2002-12-19 |
WO2002100538A8 (en) | 2003-11-20 |
WO2002100538A3 (en) | 2003-03-27 |
US20040176549A1 (en) | 2004-09-09 |
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