EP2430071A1 - Method for the continuous production of (meth)acrylic acid esters containing urethane groups - Google Patents
Method for the continuous production of (meth)acrylic acid esters containing urethane groupsInfo
- Publication number
- EP2430071A1 EP2430071A1 EP10717647A EP10717647A EP2430071A1 EP 2430071 A1 EP2430071 A1 EP 2430071A1 EP 10717647 A EP10717647 A EP 10717647A EP 10717647 A EP10717647 A EP 10717647A EP 2430071 A1 EP2430071 A1 EP 2430071A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- meth
- acrylic acid
- urethane group
- alcohol
- acid ester
- 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- Withdrawn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
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 35
- 238000010924 continuous production Methods 0.000 title description 2
- 150000001298 alcohols Chemical class 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 102000004190 Enzymes Human genes 0.000 claims abstract description 16
- 108090000790 Enzymes Proteins 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- -1 acrylic ester Chemical class 0.000 claims description 43
- 238000004821 distillation Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 108010093096 Immobilized Enzymes Proteins 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 108090001060 Lipase Proteins 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 102000004882 Lipase Human genes 0.000 claims description 11
- 239000004367 Lipase Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 235000019421 lipase Nutrition 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004808 2-ethylhexylester Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 238000005809 transesterification reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 230000002255 enzymatic effect Effects 0.000 description 8
- BSBQJOWZSCCENI-UHFFFAOYSA-N 3-hydroxypropyl carbamate Chemical compound NC(=O)OCCCO BSBQJOWZSCCENI-UHFFFAOYSA-N 0.000 description 7
- JLQQAHZVCKWXPD-UHFFFAOYSA-N 3-hydroxypropyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.NC(=O)OCCCO JLQQAHZVCKWXPD-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 229950000688 phenothiazine Drugs 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical group CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 description 2
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical group CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 2
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-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
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 108090000371 Esterases Proteins 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229960001867 guaiacol Drugs 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-methyl-PhOH Natural products CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N (R)-alpha-Tocopherol Natural products OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- ZEMODTUZIWTRPF-UHFFFAOYSA-N 1-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCNC1=CC=C(NCC)C=C1 ZEMODTUZIWTRPF-UHFFFAOYSA-N 0.000 description 1
- PVRZMTHMPKVOBP-UHFFFAOYSA-N 1-n,4-n-dimethylbenzene-1,4-diamine Chemical compound CNC1=CC=C(NC)C=C1 PVRZMTHMPKVOBP-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- FMLWUIUELCCQOB-UHFFFAOYSA-N 2,2-dimethyl-3h-1-benzofuran-7-ol Chemical compound C1=CC(O)=C2OC(C)(C)CC2=C1.C1=CC(O)=C2OC(C)(C)CC2=C1 FMLWUIUELCCQOB-UHFFFAOYSA-N 0.000 description 1
- VRMNMYMLBAVRDD-UHFFFAOYSA-N 2,3-ditert-butyl-4-methoxyphenol Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C VRMNMYMLBAVRDD-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- GWLOGZRVYXAHRE-UHFFFAOYSA-N n,4-dimethylbenzenesulfonamide Chemical compound CNS(=O)(=O)C1=CC=C(C)C=C1 GWLOGZRVYXAHRE-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NYEPSLKMENGNDO-UHFFFAOYSA-N n-tert-butyl-4-methylbenzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)NC(C)(C)C)C=C1 NYEPSLKMENGNDO-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
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- 210000000496 pancreas Anatomy 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- HBROZNQEVUILML-UHFFFAOYSA-N salicylhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1O HBROZNQEVUILML-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 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
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- AOBORMOPSGHCAX-DGHZZKTQSA-N tocofersolan Chemical compound OCCOC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C AOBORMOPSGHCAX-DGHZZKTQSA-N 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 125000005490 tosylate group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
Definitions
- the present invention relates to a process for the continuous preparation of urethane group-containing (meth) acrylic acid esters.
- the preparation of (meth) acrylic acid esters is usually carried out by acid or base-catalyzed esterification or transesterification of (meth) acrylic acid or others
- JP 2001-40039 A describes carbamate group-containing (meth) acrylic esters which are prepared via an acid-catalyzed esterification.
- a disadvantage of the described method is that the purity of the product obtained is only 75.9% at a mass balance of 95%.
- EP 136 813 A2 describes the two-stage preparation of N-substituted, carbamate group-containing acrylates by reacting polyhydroxyalkylated acrylates with isocyanates.
- a disadvantage of the method described is the limitation to such substrates, which are available as isocyanates.
- N, N-disubstituted carbamates can not be prepared by this process, likewise those having N-substituents which carry isocyanate-reactive groups.
- toxic tin compounds are also necessary as a catalyst.
- No. 5,240,835 describes the transesterification of alkyl acrylates with alcohols with catalysis of a biocatalyst from Corynebacterium oxydans.
- the reaction of a 96-fold molar excess of ethyl acrylate with 2,2-dimethyl-1,3-propanediol is listed there. Only 21% yield was obtained after 3 days at 30 0 C.
- WO 2004/05088 A1 discloses another enzyme-catalyzed preparation process of urethane group-containing (meth) acrylic acid esters.
- a disadvantage of the method described is that the products have a relatively low purity and still be processed unrefined.
- the object has been achieved by a process for preparing urethane group-containing (meth) acrylic esters (U) by reacting a urethane group-containing alcohol (A) with a (meth) acrylic ester of a saturated alcohol (G) in the presence of at least one polymerization inhibitor (P) with an enzyme (E ) as a catalyst in a reactor, wherein the (meth) acrylic acid ester of a saturated alcohol (G) with the urethane group-containing alcohol (A) continuously via at least one fixed bed reactor filled with an immobilized enzyme (E) is passed as a catalyst.
- Urethane groups in the context of this document are O-substituted and N-unsubstituted, monosubstituted or disubstituted structural elements of the formula> N-C (OO) -O-.
- (Meth) acrylic acid in this specification stands for methacrylic acid and acrylic acid, preferably for acrylic acid.
- Urethane group-containing alcohols (A) are those compounds which have at least one urethane group, preferably 1 to 10, particularly preferably 1 to 5, very particularly preferably 1 to 2 and in particular a urethane group, and at least one hydroxy group (-OH) 1 to 10, particularly preferably 1 to 6, very particularly preferably 1 to 3, in particular 1 to 2 and especially a hydroxy group.
- Preferred urethane group-containing alcohols (A) have an average molecular weight of 105 to 800,000 g / mol, preferably up to 25,000, more preferably 5,000 and most preferably up to 4,500 g / mol.
- Particularly preferred urethane group-containing alcohols (A) are those obtainable by a) reacting an amine with a carbonate and b) optionally purifying the reaction mixture obtainable from a).
- Very particularly preferred urethane group-containing alcohols (A) are those obtainable by the following reaction equation
- R 1 , R 2 are independently hydrogen, Ci-Cis-alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C2-Ci8-alkyl, C2-Ci8-alkenyl, C6 -Ci2-aryl, C5-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, wherein the radicals mentioned in each case by aryl, alkyl, aryloxy, alkoxy, heteroatome and / or heterocycles, or a group of the formula - [X,] kH,
- R 1 and R 2 can also form a ring together.
- R 1 and R 2 are independently hydrogen, Ci-Ci 2 alkyl, Cs-C ⁇ -cycloalkyl or a group of the formula - [X,] kH, more preferably R 1 and R 2 are independently hydrogen, Ci-C 4 -AlkVl, Cs-C ⁇ -cycloalkyl or a group of the formula - [X,] kH and most preferably hydrogen, Ci-C 4 -AlkVl, or a group of the formula - [X,] kH.
- one of the radicals R 1 and R 2 is hydrogen and the other C 1 -C 4 -alkyl, or a group of the formula - [X,] kH.
- Preferred X are -CH 2 -CH 2 -O-, -CH 2 -CH 2 -N (H) -, -CH 2 -CH 2 -CH 2 -N (H) -, -CH 2 -CH (NH 2 ) -, -CH 2 -CH (NHCHO) -, -CH 2 -CH (CHs) -O- and -CH (CHs) -CH 2 -O-, more preferably -CH 2 -CH 2 -O- , -CH 2 -CH 2 -N (H) -, -CH 2 -CH 2 -CH 2 -N (H) - and -CH 2 -CH (NH 2 ) -, very particularly preferably -CH 2 -CH 2 -O-, -CH 2 -CH 2 -N (H) - and -CH 2 -CH 2 -CH 2 -N (H) -.
- k is preferably 1 to 30, particularly
- R 1 and / or R 2 are hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-butyl Octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 2-hydroxyethyl, 2-hydroxypropyl, 1 Hydroxypropyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa-octyl or 1 1-hydroxy-3,6,9-trioxa
- Y is preferably C 2 -C 10 -alkylene, particularly preferably C 2 -C 6 -alkylene, very particularly preferably C 2 -C 4 -alkylene, in particular C 2 -C 3 -alkylene and especially C 2 -C 4 -alkylene, where the radicals mentioned are in each case represented by aryl, alkyl, aryloxy, Alkyloxy, heteroatoms and / or heterocycles can be substituted.
- Examples of Y are 1, 2-ethylene, 1, 2-propylene, 1, 1-dimethyl-1, 2-ethylene, 1
- Exemplary amines are ammonia, methylamine, dimethylamine, ethylamine, diethylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tert-butylamine, monoethanolamine, diethanolamine, propanolamine, dipropanolamine, piperidine, piperazine , Pyrrolidine, cyclopentylamine, cyclohexylamine, aniline, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polymers with amine function as described in WO 04/050888 A1 on page 5, from line 28 to page 6, line 33.
- Exemplary carbonates are ethylene carbonate, 1, 3-propylene carbonate and 1, 2-propylene carbonate.
- Preferred urethane group-containing alcohols (A) are those compounds as disclosed in German Offenlegungsschrift DE 10 2005 016 225 A1. Of the binary mixtures of structurallyomeric ⁇ -hydroxyalkylcarabamates mentioned therein, the isomer mixture of hydroxypropyl carbamate is particularly preferred for the process according to the invention. Hydroxypropylcarbamate is obtained by reacting 1, 2-propylene carbonate with ammonia according to DE 10 2005 016 255 A1.
- the reaction of the amine with the carbonate is known per se, for example from US 4,820,830 B, column 4, line 44 to column 5, line 9, and not limited.
- the amine and the carbonate in a stoichiometry of 0.7 to 1.2 moles of amine: 1 mol of carbonate, preferably 0.8 to 1, 2: 1, more preferably 0.9 to 1, 1: 1, very particularly preferably 0.95 - 1, 1: 1 and in particular 1: 1 mol / mol reacted with each other.
- the reaction is generally carried out at a temperature of from 0 to 120 ° C., especially from 20 to 100, very particularly preferably from 30 to 80 and very particularly preferably from 40 to 80 ° C.
- the reaction is generally completed within 12 hours, preferably within 15 minutes to 10 hours, more preferably in 30 minutes to 8 hours, most preferably 45 minutes to 6 hours, and especially within 1 to 4 hours.
- the total amine number acc. DIN 53176 of the urethane group-containing alcohol (A) should not be more than 200 mg KOH / g, preferably not more than 100 and most preferably not more than 80 mg KOH / g.
- reaction of the amine with the carbonate can be carried out without solvent or in the presence of such, for example, alcohols, ethers, ketones, hydrocarbons or water, preferably without solvent.
- the urethane group-containing alcohol (A) can be purified in a further step, for example by filtration, distillation, rectification, chromatography, treatment with ion exchangers, adsorbents, neutral, acidic and / or alkaline washing, stripping or crystallization.
- the urethane group-containing alcohol (A) can be used purified.
- the urethane-containing alcohol (A) is continuously separated by a pure distillation of low-boiling and high-boiling secondary components.
- the lower-boiling components are, for example, unreacted carbonate or the corresponding diols.
- high boilers are higher molecular weight secondary components into consideration, which are responsible for the color.
- the purifying distillation is carried out continuously in the fine vacuum range, ie at a reduced pressure of 1 to 100 mbar, preferably 1 to 50 mbar, more preferably 1 to 20 mbar and in particular in the range of 1 to 10 mbar.
- the temperature in the purification by distillation is usually in the range of 50 to 200 0 C, preferably in the range of 75 to 180 0C, and particularly preferably in the range of 100 to 160 0 C. is due to the short residence times and relatively low thermal load Compared to the discontinuous distillation, a highly pure urethane group-containing alcohol (A) achievable.
- (Meth) acrylic esters of a saturated alcohol (G) are preferably those esters of (meth) acrylic acid with a saturated Ci-Cio-alcohol.
- Examples of compounds (G) are (meth) acrylic acid methyl, -ethyl, -n-butyl, -iso- butyl, n-octyl and 2-ethylhexyl ester, 1, 2-ethylene glycol di- and mono (meth) acrylate, 1, 4-butanediol di- and mono (meth) acrylate, 1, 6-hexanediol di- and mono (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate.
- Ethylhexylester and most preferably (meth) acrylic acid methyl, ethyl and n-butyl ester.
- Enzymes (E) which can be used according to the invention are selected, for example, from hydrolases, esterases (EC 3.1.-.-), lipases (EC 3.1.1.3), glycosylases (EC 3.2.-.-) and proteases (EC 3.4.-.-) in free or immobilized on a carrier chemically or physically immobilized form, preferably lipases, esterases or proteases.
- Novozym ® 435 lipase from Candida antartica B
- lipase from Aspergillus sp. Aspergillus niger sp., Mucor sp.
- Penicillium cyclopium sp. Geotricum candidum sp.
- Rhizopus javanicus Burkholderia sp.
- Candida sp are., Pseudomonas sp., Or
- Porcine pancreas are lipase from Candida antartica B or from Burholderia sp.
- the (meth) acrylic ester of the saturated alcohol (G) with the urethane group-containing alcohol (A) are previously mixed together, and this reaction mixture is then passed through the at least one fixed bed reactor filled with an immobilized enzyme (E).
- the reactants can also be passed separately from one another simultaneously via the immobilized enzyme (E).
- a reaction mixture of (meth) acrylic acid ester (G) and urethane group-containing alcohol (A) is first prepared, which is then passed over the immobilized enzyme (E).
- the molar ratio of (meth) acrylic ester of a saturated alcohol (G) (based on the (meth) acrylic units) to urethane group-containing alcohol (A) (relative to hydroxy groups) can be varied over a wide range, e.g. in the ratio 100: 1 to 1: 1, preferably 50: 1 to 1: 1, more preferably 20: 1 to 1: 1 and most preferably 10: 1 to 1: 1, vary.
- the enzyme (E) is immobilized on a suitable support in the method according to the invention.
- immobilizing enzymes There are five classical methods of immobilizing enzymes, namely adsorption, covalent bonding, membrane entrapment, gel entrapment and cross-linking.
- different carrier materials can be used, wherein the chemical interactions of the carrier surface with the enzyme must be adjusted so that no unwanted side effects, such as inactivation occur.
- various inorganic and organic materials are suitable as solid carriers, the latter being of natural or synthetic origin. Inorganic carriers usually have high pressure stability, while organic carriers show good chemical stability.
- the inorganic carriers used are predominantly porous materials based on silicon or aluminum oxides or mixtures thereof.
- Natural organic carriers are, for example, polysaccharides such as cellulose, starch, dextran, agarose and chitin. But also proteins like collagen, gelatine and albumin are used.
- Synthetic organic polymers are poly (meth) acrylates, polyacrylamides, vinyl and allyl polymers, polyesters or polyamides.
- enzymes which are already immobilized on a suitable support preference is given to using enzymes which are already immobilized on a suitable support.
- immobilized enzymes preferably lipases, under the trade name Novozym ® 435 (lipase from Candida antartica B) are available from the company Novozymes.
- the immobilized enzyme is provided in a device suitable as a fixed bed reactor, for example a tube or a column. Subsequently, the reactants or preferably the premixed reaction mixture of a (meth) acrylic acid ester (G) and a urethane group-containing alcohol (A) are pumped by means of a pump over the fixed bed reactor charged with the immobilized enzyme.
- a device suitable as a fixed bed reactor for example a tube or a column.
- the enzymatic transesterification with a (meth) acrylic ester of a saturated alcohol (G) is generally carried out at 0 to 100 0 C, preferably 20 to 80 0 C, more preferably 20 to 70 0 C, most preferably 20 to 60 0 C.
- the reaction can take place in organic solvents or mixtures thereof or without the addition of solvents.
- the batches are generally largely anhydrous (i.e., below 10, preferably below 5, more preferably below 1% by volume of water additive).
- the proportion of organic solvents is for example 0.01-30 wt .-%, preferably 0.1-5 wt .-%.
- Suitable organic solvents are known for this purpose, for example tertiary monools, such as Cs-C ⁇ alcohols, preferably tert-butanol, tert-amyl alcohol, pyridine, poly-Ci-C4-alkylenglykoldi-Ci-C4-alkyl ethers, preferably Polyethylenglycoldi-Ci C 4 -alkyl ethers, such as, for example, 1, 2-dimethoxyethane, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether 500, C 1 -C 4 -alkylene carbonates, in particular in particular propylene carbonate, Cs-C ⁇ -alkylacetic acid esters, in particular tert-butylacetic acid esters, THF, toluene, 1,3-dioxolane,
- aqueous solvents can be added to the organic solvents, so that - depending on the organic solvent - single- or multi-phase reaction solutions.
- aqueous solvents are water as well as aqueous, dilute (e.g., 10 to 100 mM) buffers, for example, having a pH in the range of about 6 to 8, e.g. Potassium phosphate or TRIS-HCl buffer.
- the proportion of water in the reaction mixture is usually 0-10% by volume.
- the reactants are preferably used without pretreatment (drying, water doping).
- the enzymatic transesterification is carried out without the addition of water and organic solvents.
- the reaction is carried out continuously via at least one fixed bed reactor filled with an immobilized enzyme (E).
- the reactants or the premixed reaction mixture are pumped from a receiver vessel by means of a pump over the fixed bed reactor charged with the immobilized enzyme.
- the resulting crude product containing the urethane group-containing (meth) acrylic ester (U) is collected in a suitable storage vessel.
- the crude product is first purified by distillation, the azeotrope being freed from saturated saturated alcohol and excess corresponding (meth) acrylic ester (G) and optionally used entrainer via a connected distillation column.
- an additional entrainer which forms an azeotrope with the liberated saturated alcohol and the excess of corresponding (meth) acrylic acid ester (G). It is preferably an entraining agent whose azeotrope formed with the saturated alcohol liberated and the excess corresponding corresponding (meth) acrylic ester (G) shows a phase decay or which can be broken by addition of water.
- suitable entrainers are, for example, n-pentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and any mixtures thereof.
- the distillation column used for the separation of the azeotrope is of a known type and has the usual internals.
- column internals men in principle all common installations into consideration, for example, soils, packings and / or beds. Of the soils, bubble-cap trays, sieve trays, valve trays, Thormann trays and / or dual / flow trays are preferred; of the trays, those with rings, spirals, saddles or braids are preferred. As a rule, 5 to 20 theoretical plates are sufficient.
- the distilled azeotrope is then condensed in a condenser of conventional design.
- the capacity of the pump to pump the reaction mixture over the fixed bed reactors charged with immobilized enzyme is adjusted to achieve the thermodynamic equilibrium state at the outlet of the enzyme fixed bed.
- the urethane group-containing (meth) acrylic acid ester is subjected to an extraction process after leaving the at least one fixed bed reactor charged with immobilized enzyme (E) and before collecting in the storage vessel.
- the extraction is usually carried out with water, wherein the remaining urethane group-containing alcohol (A) passes into the aqueous phase and is thus separated from the final product.
- the organic phase containing urethane group-containing (meth) acrylic acid ester (U) and optionally remaining (meth) acrylic acid ester (G) can be purified in a previously described distillation column, wherein the (meth) acrylic acid ester (G) is separated as low boilers from the final product.
- the separation from the organic solvent is usually carried out by distillation, rectification or in the case of solid reaction products by filtration.
- a chromatography or a purifying distillation can also be carried out.
- the urethane group-containing (meth) acrylic ester (U) is isolated from the bottom obtained from the solvent distillation, if appropriate, in a further distillation step as top product and with at least one of the below Stabilized polymerization inhibitors.
- stabilizers mentioned there hydroquinone monomethyl ether and phenothiazine are particularly suitable for the purifying distillation.
- the rectification column useful for this distillation step is of known type, such as packed columns, packed columns, or tray columns, and has separable internals (e.g., bell, sieve, or dual-flow trays) or contains beds or directional packing. These conventional internals preferably have 10 to 20 theoretical plates. Thin-film evaporators are also suitable. Evaporator and condenser are also conventional design.
- the urethane (meth) is preferably acrylate (U) at a bottom temperature from 100 to 140 0 C, preferably 110-130 0 C and a head pressure of 1 to 100 mbar, preferably from 1 to 50 mbar, particularly preferably from 1 to 10 mbar and in particular from 1 to 5 mbar.
- a solution of 0.05-0.5% hydroquinone monomethyl ether or another similarly effective storage stabilizer may be sprayed into the condenser, the amount being chosen such that the condensate has a storage stabilizer concentration of 10-20 ppm.
- a portion of the condensate, preferably 10-20%, can be returned to the column as reflux.
- the resulting urethane group-containing (meth) acrylic ester (U) has, according to the gas chromatographic analysis, a purity of at least 98.5%, preferably at least 99.0% and particularly preferably at least 99.5%.
- the bottom product of the purifying distillation which consists mainly of residual urethane (meth) acrylate (U), Michael addition products, stabilizer and polymers can be passed into a residue distillation and / or residue splitting.
- the pure urethane group-containing (meth) acrylic acid ester (U) is discharged via a side draw, preferably gaseous, in the lower column region, preferably in the lower half, more preferably in the lower third, condensed and stabilized as described above.
- reaction conditions in the enzymatic transesterification are mild. Due to the low temperatures and other mild conditions, the formation of by-products in the transesterification is avoided, which may otherwise be derived, for example, from chemical catalysts or by unwanted radical polymerization of the (meth) acrylates used (G), which can otherwise be prevented only by the addition of stabilizers ,
- the transesterification according to the invention takes place in the presence of at least one polymerization inhibitor (P).
- P polymerization inhibitor
- Suitable polymerization inhibitors (P) may for example be N-oxides (nitroxyl or N-oxyl radicals, ie compounds which have at least one> N-0 group), such as. 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-0x0-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2,2,6,6- tetramethyl-piperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4,4 ', 4 "-tris (2,2,6,6-tetramethyl-piperidine-N-oxyl) -phosphite or 3-0x0-2,2, 5, 5-tetramethylpyrrolidine-N-oxyl; mono- or polyhydric phenols which optionally have one or more alkyl groups, such as, for example, alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butyl
- Ethoxyphenol 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl-4-methoxyphenol; Tocipherole, such as. B. ⁇ -tocopherol and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxy-coumaran), a- aromatic amines, such as. N, N-diphenylamine or N-nitroso-diphenylamine; Phenylenediamine, such as. B.
- N, N'-dialkyl-p-phenylenediamine wherein the alkyl radicals may be the same or different and each independently consist of 1 to 4 carbon atoms and may be straight or branched, such as.
- methylethylimine or methylene violet sulfonamides, such as.
- oximes such as Aldoxime, Ketoxime or amidoximes, such as.
- Triphenyl phosphite triethyl phosphite, hypophosphorous acid or alkyl esters of phosphorous acids; sulfur compounds such. Diphenyl sulfide or phenothiazine; Metal salts such as copper or manganese, cerium, nickel, chromium salts, for example chlorides, sulfates, salicylates, tosylates, acrylates or acetates, such as. Copper acetate, copper (II) chloride, copper salicylate, cerium (III) acetate or cerium (III) ethylhexanoate, or mixtures thereof.
- Metal salts such as copper or manganese, cerium, nickel, chromium salts, for example chlorides, sulfates, salicylates, tosylates, acrylates or acetates, such as. Copper acetate, copper (II) chloride, copper salicylate, cerium (III) acetate or cerium (
- polymerization inhibitor at least one compound from the group hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine N-oxyl, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4 -dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-methyl-4-tert-butylphenol, hypophosphorous acid, copper acetate, copper (II) chloride, copper salicylate and cerium (III) acetate.
- an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) will preferably be present.
- urethane group-containing (meth) acrylic esters (U) of the formula (I) are obtainable by the process according to the invention.
- R 1 and R 2 have the meanings given above,
- Y is selected from 1, 2-ethylene, 1, 2-propylene, 1, 1-dimethyl-1, 2-ethylene, 1
- R 3 is hydrogen or methyl, preferably hydrogen, with the proviso that at least one of the radicals R 1 and R 2 is not hydrogen.
- the available urethane group-containing (meth) acrylic esters (U) can advantageously be used as comonomers in poly (meth) acrylates or as reactive diluents in radiation-curable and / or dual-cure poly (meth) acrylates.
- Such poly (meth) acrylates are suitable as binders in radiation or dual-cure coating agents.
- available coatings have very high scratch resistance, hardness, chemical resistance, elasticity and adhesion to both hydrophilic and hydrophobic substrates.
- a further use of the urethane group-containing (meth) acrylic esters (U) prepared by the process according to the invention is possible as an additive in coating formulations.
- the urethane group-containing (meth) acrylic esters (U) can be used both in basecoats and in topcoats. Because of their particular properties, such as increasing the scratch resistance and elasticity, as well as the lowering of the viscosity, especially in branched polyacrylates, a radiation-cured clearcoat, their use in topcoats is preferred.
- the urethane group-containing (meth) acrylic ester (U) may be suitably blended with a solvent additive to prevent the solid state and to keep the urethane group-containing (meth) acrylic acid ester (U) in the liquid phase.
- a solvent additive to prevent the solid state and to keep the urethane group-containing (meth) acrylic acid ester (U) in the liquid phase.
- Miscible lower hydrocarbons such as methanol, ethanol, propanol, isopropanol, butanol, hexanol and any mixtures thereof are suitable for this purpose.
- Wt .-% preferably 5 to 30 wt .-% and particularly preferably 10 to 20 wt .-% of a suitable solvent, in each case based on the total weight of solvent and urethane group-containing (meth) acrylic acid ester (U) used.
- the transesterification of ethyl acrylate with hydroxypropyl carbamate was carried out in a receiving vessel with attached double-walled glass column, pump and subsequent 5 liter storage vessel.
- the double-walled glass column (length 40 cm, diameter 1, 35 cm) was charged with 14 mL of lipase (Novozym ® 435). Then, 2002.4 g (20.0 mol) of ethyl acrylate and 248.9 g (2.0 mol) of the previously purified hydroxypropyl carbamate were mixed together in the master vessel.
- 400.5 mg (200 ppm, based on ethyl acrylate) of hydroquinone monomethyl ether were added. The temperature was adjusted to 40 ° C. Subsequently, with the aid of the pump, the initially charged reaction mixture was pumped through the enzyme-loaded double-walled glass column at a rate of 1 1 ml per hour and collected in the storage vessel.
- Example 1 was repeated. However, the pump was operated at a rate of 15 mL / h. The reaction time was a total of about 310 h, after different time intervals of the output in the storage vessel, the conversion and the purity were determined by GC analysis. The results are summarized in Table 1. Table 1
- Example 2 From the effluent of Example 2 with a purity of 52.9%, 250 g (containing 0.9 mol of hydroxypropyl carbamate) were removed and admixed with 2010 g (20.08 mol) of ethyl acrylate. At a temperature of 40 0 C the mixture via a second, with 12 mL of lipase (Novozym ® 435) was charged jacketed glass column (length 35 cm 40 cm, diameter 1) guided by means of a pump at a rate of 15 mL / h. The reaction time was a total of about 160 h, wherein after various time intervals, the discharge in the storage vessel, the conversion and the purity were determined by GC analysis. The results are summarized in Table 2.
- the entire effluent after completion of the reaction was collected in a 2.5 L miniature flask.
- the crude product contained 70.2% hydroxypropylcarbamate acrylate according to GC analysis.
- the tube product was then washed with 491 g of deionized water. This gave 503.4 g of aqueous phase and an organic phase containing 87.7% hydroxypropyl carbamate according to GC analysis.
- Example 1 was repeated.
- the reaction temperature was set to 60 0 C.
- the pump was operated at a rate of 15 mL / h.
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Abstract
The invention relates to a method for producing (meth)acrylic acid esters (U) containing urethane groups by reacting an alcohol containing urethane groups (A) with a (meth)acrylic acid ester of a saturated alcohol (G) in the presence of at least one polymerisation inhibitor (P), and an enzyme (E) used as a catalyst, in a reactor. Said (meth)acrylic acid ester of a saturated alcohol (G) is continuously guided with alcohol containing the urethane groups (A) on at least one solid bed reactor filled with an immobilised enzyme (E) used as a catalyst.
Description
Verfahren zur kontinuierlichen Herstellung von urethangruppenhaltigen (Meth)acrylsäureestern Process for the continuous production of urethane group-containing (meth) acrylic acid esters
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur kontinuierlichen Herstellung von urethangruppenhaltigen (Meth)acrylsäureestern.The present invention relates to a process for the continuous preparation of urethane group-containing (meth) acrylic acid esters.
Die Herstellung von (Meth)acrylsäureestern erfolgt zumeist durch säure- oder basenka- talysierte Ver- oder Umesterung von (Meth)acrylsäure oder anderenThe preparation of (meth) acrylic acid esters is usually carried out by acid or base-catalyzed esterification or transesterification of (meth) acrylic acid or others
(Meth)acrylsäureestern mit Alkoholen bei Temperaturen von 40 bis deutlich über 100 0C. Aufgrund der hohen Temperaturen ist der Zusatz hoher Mengen von Polymerisationsinhibitoren erforderlich, um eine unerwünschte Polymerisierung der Monomeren zu unterdrücken. Dabei entstehen oft komplexe und bisweilen gefärbte Produktgemi- sehe. Zur Entfernung von Färbungen und unumgesetzter Reaktanden werden die Produktgemische durch aufwendige alkalische Wäschen aufgearbeitet. Das Waschverfahren ist langwierig und kostspielig, da sich vor allem teilveresterte Produkte nur langsam extrahieren und abtrennen lassen.(Meth) acrylic acid esters with alcohols at temperatures of 40 to well above 100 0 C. Due to the high temperatures, the addition of high amounts of polymerization inhibitors is required to suppress unwanted polymerization of the monomers. This often results in complex and sometimes colored product mixtures. To remove dyeings and unreacted reactants, the product mixtures are worked up by expensive alkaline washes. The washing process is tedious and costly, because especially partially esterified products extract only slowly and can be separated.
Die Herstellung urethangruppenhaltiger (Meth)acryate über eine konventionelle säurekatalysierte Veresterung ist zudem schwierig, da Urethangruppen säureempfindlich sind.Moreover, the preparation of urethane group-containing (meth) acrylates by conventional acid-catalyzed esterification is difficult because urethane groups are acid-sensitive.
JP 2001-40039 A beschreibt carbamatgruppenhaltige (Meth)acrylsäureester, die über eine säurekatalysierte Veresterung hergestellt werden. Nachteilig an dem beschriebenen Verfahren ist, dass die Reinheit des erhaltenen Produkts lediglich 75,9 % bei einer Massenbilanz von 95 % beträgt.JP 2001-40039 A describes carbamate group-containing (meth) acrylic esters which are prepared via an acid-catalyzed esterification. A disadvantage of the described method is that the purity of the product obtained is only 75.9% at a mass balance of 95%.
EP 136 813 A2 beschreibt die zweistufige Herstellung N-substituierter, carbamatgrup- penhaltiger Acrylate durch Umsetzung von mehrfach hydroxyalkylierten Acrylaten mit Isocyanaten. Nachteilig an dem beschriebenen Verfahren ist die Beschränkung auf solche Substrate, die als Isocyanate verfügbar sind. So sind beispielsweise N, N- disubstituierte Carbamate nach diesem Verfahren nicht herstellbar, ebenfalls solche mit N-Substituenten, die gegenüber Isocyanat reaktive Gruppen tragen. Für die Um- setzung mit dem Isocyanat sind zudem toxische Zinnverbindungen als Katalysator notwendig.EP 136 813 A2 describes the two-stage preparation of N-substituted, carbamate group-containing acrylates by reacting polyhydroxyalkylated acrylates with isocyanates. A disadvantage of the method described is the limitation to such substrates, which are available as isocyanates. Thus, for example, N, N-disubstituted carbamates can not be prepared by this process, likewise those having N-substituents which carry isocyanate-reactive groups. For the reaction with the isocyanate, toxic tin compounds are also necessary as a catalyst.
Die Herstellung von (Meth)acrylsäureestern durch eine enzymatische Ver- oder U- mesterung ist bekannt.The preparation of (meth) acrylic acid esters by an enzymatic esterification or urea esterification is known.
Hajjar et al. beschreiben in Biotechnol. Lett. 1990, 12, 825-830 die enzymatische U- mesterung von cyclischen und offenkettigen Alkandiolen mit Ethylacrylat mit einer Li- pase aus Chromobacterium viscosum. Die Reaktionen laufen bei einem 18-fachen
molaren Überschuss des Alkylacrylats gegenüber dem Diol in einem lösungsmittelfreien System ab. Es entstehen Mischungen aus Mono- und Diacrylaten.Hajjar et al. describe in Biotechnol. Lett. 1990, 12, 825-830 describe the enzymatic transesterification of cyclic and open-chain alkanediols with ethyl acrylate with a lipase from Chromobacterium viscosum. The reactions run at an 18-fold molar excess of the alkyl acrylate relative to the diol in a solvent-free system. This results in mixtures of mono- and diacrylates.
US 5,240,835 beschreibt die Umesterung von Alkylacrylaten mit Alkoholen unter Kata- lyse eines Biokatalysators aus Corynebacterium oxydans. Beispielhaft wird dort die Reaktion von einem 96-fachen molaren Überschuss Ethylacrylat mit 2,2-Dimethyl-1 ,3- propandiol aufgeführt. Lediglich 21 % Ausbeute wurden nach 3 Tagen bei 30 0C erhalten.No. 5,240,835 describes the transesterification of alkyl acrylates with alcohols with catalysis of a biocatalyst from Corynebacterium oxydans. By way of example, the reaction of a 96-fold molar excess of ethyl acrylate with 2,2-dimethyl-1,3-propanediol is listed there. Only 21% yield was obtained after 3 days at 30 0 C.
Derango et al. beschreiben in Biotechnol. Lett. 1994, 16, 241-246 die Lipase- katalysierte Herstellung von Carbamoyloxyethylmethacrylat durch Umesterung von 2- Hydroxyethylcarbamat mit Vinylmethacrylat. Eine vollständige Umsetzung wird erreicht durch das spezielle Edukt Vinylmethacrylat, da freigesetzter Vinylalkohol dem Reaktionsgleichgewicht als Acetaldehyd entzogen wird. Nachteilig an diesem Verfahren ist, dass Vinylmethacrylat nicht kommerziell verfügbar ist.Derango et al. describe in Biotechnol. Lett. 1994, 16, 241-246, the lipase-catalyzed preparation of carbamoyloxyethyl methacrylate by transesterification of 2-hydroxyethyl carbamate with vinyl methacrylate. A complete reaction is achieved by the specific starting material vinyl methacrylate, since liberated vinyl alcohol is removed from the reaction equilibrium as acetaldehyde. A disadvantage of this process is that vinyl methacrylate is not commercially available.
Aus WO 2004/05088 A1 ist ein weiteres enzymkatalysiertes Herstellungsverfahren urethangruppenhaltiger (Meth)acrylsäureester bekannt. Nachteilig an dem beschriebenen Verfahren ist, dass die Produkte eine relativ geringe Reinheit aufweisen und den- noch ungereinigt weiterverarbeitet werden.WO 2004/05088 A1 discloses another enzyme-catalyzed preparation process of urethane group-containing (meth) acrylic acid esters. A disadvantage of the method described is that the products have a relatively low purity and still be processed unrefined.
Weiterhin ist an den beschriebenen Verfahren nachteilig, dass die Umesterung diskon- tinuierlilch erfolgt, was für eine Herstellung urethangruppenhaltiger (Meth)acrylsäureester in großem Maßstab unvorteilhaft ist.Furthermore, it is disadvantageous in the processes described that the transesterification takes place in a discontinuous manner, which is unfavorable for the preparation of urethane group-containing (meth) acrylic esters on a large scale.
Aufgabe der vorliegenden Erfindung war es daher, ein alternatives Verfahren zur Verfügung zu stellen, mit dem urethangruppenhaltige (Meth)acrylsäureester kontinuierlich aus einfachen, wirtschaftlich zugänglichen Edukten herstellbar sind.It was therefore an object of the present invention to provide an alternative process with which urethane group-containing (meth) acrylic esters can be prepared continuously from simple, economically available starting materials.
Die Aufgabe wurde gelöst durch ein Verfahren zur Herstellung urethangruppenhaltiger (Meth)acrylsäureester (U) durch Umsetzung eines urethangruppenhaltigen Alkohols (A) mit einem (Meth)acrylsäureester eines gesättigten Alkohols (G) in Gegenwart mindestens eines Polymerisationsinhibitors (P) mit einem Enzym (E) als Katalysator in einem Reaktor, wobei der (Meth)acryläureester eines gesättigten Alkohols (G) mit dem urethangruppenhaltigen Alkohol (A) kontinuierlich über mindestens einen Festbettreaktor gefüllt mit einem immobilisierten Enzym (E) als Katalysator geleitet wird.The object has been achieved by a process for preparing urethane group-containing (meth) acrylic esters (U) by reacting a urethane group-containing alcohol (A) with a (meth) acrylic ester of a saturated alcohol (G) in the presence of at least one polymerization inhibitor (P) with an enzyme (E ) as a catalyst in a reactor, wherein the (meth) acrylic acid ester of a saturated alcohol (G) with the urethane group-containing alcohol (A) continuously via at least one fixed bed reactor filled with an immobilized enzyme (E) is passed as a catalyst.
Mit Hilfe des erfindungsgemäßen Verfahrens ist die Herstellung urethangruppenhaltiger (Meth)acrylsäureester unter milden Bedingungen möglich. Weiterhin tritt keine we- sentliche Polymerisatbildung auf. Besonders vorteilhaft an dem erfindungsgemäßen Verfahren ist, dass die urethangruppenhaltigen (Meth)acrylsäureester durch eine en- zymatische Umesterung kontinuierlich erhalten werden, was ihre Herstellung in große-
rem Maßstab zugänglich macht.With the aid of the process according to the invention, it is possible to produce urethane group-containing (meth) acrylic acid esters under mild conditions. Furthermore, no significant polymer formation occurs. It is particularly advantageous in the process according to the invention that the (meth) acrylic acid esters containing urethane groups are continuously obtained by an enzymatic transesterification, which means that they can be prepared in large quantities. rem scale accessible.
Urethangruppen im Sinne dieser Schrift sind O-substituierte und N-un-, mono- oder disubstituierte Strukturelemente der Formel >N-C(=O)-O-.Urethane groups in the context of this document are O-substituted and N-unsubstituted, monosubstituted or disubstituted structural elements of the formula> N-C (OO) -O-.
(Meth)acrylsäure steht in dieser Schrift für Methacrylsäure und Acrylsäure, bevorzugt für Acrylsäure.(Meth) acrylic acid in this specification stands for methacrylic acid and acrylic acid, preferably for acrylic acid.
Gesättigt bedeutet im Rahmen dieser Schrift Verbindungen ohne C-C- Mehrfachbindungen (außer selbstverständlich die C=C-Doppelbindung in den (Meth)acryleinheiten).Saturated in this document means compounds without C-C multiple bonds (except, of course, the C = C double bond in the (meth) acrylic moieties).
Urethangruppenhaltige Alkohole (A) sind solche Verbindungen, die mindestens eine Urethangruppe, bevorzugt 1 bis 10, besonders bevorzugt 1 bis 5, ganz besonders be- vorzugt 1 bis 2 und insbesondere eine Urethangruppe, sowie mindestens eine Hydro- xygruppe (-OH), bevorzugt 1 bis 10, besonders bevorzugt 1 bis 6, ganz besonders bevorzugt 1 bis 3, insbesondere 1 bis 2 und speziell eine Hydroxygruppe enthalten.Urethane group-containing alcohols (A) are those compounds which have at least one urethane group, preferably 1 to 10, particularly preferably 1 to 5, very particularly preferably 1 to 2 and in particular a urethane group, and at least one hydroxy group (-OH) 1 to 10, particularly preferably 1 to 6, very particularly preferably 1 to 3, in particular 1 to 2 and especially a hydroxy group.
Bevorzugte urethangruppenhaltige Alkohole (A) weisen ein durchschnittliches Molge- wicht von 105 bis 800 000 g/mol auf, bevorzugt bis 25 000, besonders bevorzugt 5 000 und ganz besonders bevorzugt bis 4 500 g/mol.Preferred urethane group-containing alcohols (A) have an average molecular weight of 105 to 800,000 g / mol, preferably up to 25,000, more preferably 5,000 and most preferably up to 4,500 g / mol.
Besonders bevorzugte urethangruppenhaltige Alkohole (A) sind solche, die erhältlich sind durch a) Umsetzung eines Amins mit einem Carbonat und b) gegebenenfalls Aufreinigung des aus a) erhältlichen Reaktionsgemisches.Particularly preferred urethane group-containing alcohols (A) are those obtainable by a) reacting an amine with a carbonate and b) optionally purifying the reaction mixture obtainable from a).
Geeignete Amine für diese Umsetzung sind dabei Ammoniak, primäre oder sekundäre Amine, Carbonate sind O,O'-disubstituierte Carbonate mit dem Strukturemelement -O-C(=O)-O-.Suitable amines for this reaction are ammonia, primary or secondary amines, carbonates are O, O'-disubstituted carbonates having the structural element -O-C (= O) -O-.
Ganz besonders bevorzugte urethangruppenhaltige Alkohole (A) sind solche, die nach der folgenden Reaktionsgleichung erhältlich sindVery particularly preferred urethane group-containing alcohols (A) are those obtainable by the following reaction equation
worin
R1, R2 unabhängig voneinander Wasserstoff, Ci-Cis-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C2-Ci8-Alkyl, C2-Ci8-Alkenyl, C6-Ci2-Aryl, C5-Ci2-Cycloalkyl oder einen fünf- bis sechsgliedri- gen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyc- lus, wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, He- teroatome und/oder Heterocyclen substituiert sein können, oder eine Gruppe der Formel -[X,]k-H,wherein R 1 , R 2 are independently hydrogen, Ci-Cis-alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C2-Ci8-alkyl, C2-Ci8-alkenyl, C6 -Ci2-aryl, C5-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, wherein the radicals mentioned in each case by aryl, alkyl, aryloxy, alkoxy, heteroatome and / or heterocycles, or a group of the formula - [X,] kH,
Xi für jedes i = 1 bis k unabhängig voneinander ausgewählt sein kann aus der Gruppe -CH2-CH2-O-, -CH2-CH2-N(H)-, -CH2-CH2-CH2-N(H)-, -CH2-CH(NH2)-, -CH2-CH(NHCHO)-, -CH2-CH(CHs)-O-, -CH(CHs)-CH2-O-, -CH2-C(CHs)2-O-, -C(CHs)2-CH2-O-, -CH2-CH2-CH2-O-, -CH2-CH2-CH2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O- und -CHPh-CH2-O-, worin Ph für Phenyl und Vin für Vinyl steht,Xi for each i = 1 to k can be independently selected from the group -CH 2 -CH 2 -O-, -CH 2 -CH 2 -N (H) -, -CH 2 -CH 2 -CH 2 -N (H) -, -CH 2 -CH (NH 2 ) -, -CH 2 -CH (NHCHO) -, -CH 2 -CH (CHs) -O-, -CH (CHs) -CH 2 -O-, -CH 2 -C (CHs) 2 -O-, -C (CHs) 2 -CH 2 -O-, -CH 2 -CH 2 -CH 2 -O-, -CH 2 -CH 2 -CH 2 -CH 2 -O-, -CH 2 -CHVin-O-, -CHVin-CH 2 -O-, -CH 2 -CHPh-O- and -CHPh-CH 2 -O-, wherein Ph is phenyl and Vin is vinyl .
k für eine Zahl von 1 bis 50 undk for a number from 1 to 50 and
Y C2-C2O-AI kylen oder durch ein- oder mehrere Sauerstoff- und/oder Schwefel- atome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen und/oder durch eine oder mehrere -(CO)-, -0(CO)O-, -(NH)(CO)O-, -0(CO)(NH)-, -0(CO)- oder -(CO)O-Gruppen unterbrochenes C2-C20-Al kylen, wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, Hetero- atome und/oder Heterocyclen substituiert sein können,YC 2 -C 2 O-Al kylene or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more - (CO) -, -0 (CO ) O-, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O- groups interrupted C 2 -C 20 alkylene, wherein the each of these radicals may be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
bedeuten.mean.
R1 und R2 können auch gemeinsam einen Ring bilden.R 1 and R 2 can also form a ring together.
Bevorzugt sind R1 und R2 unabhängig voneinander Wasserstoff, Ci-Ci2-Alkyl, Cs-Cβ- Cycloalkyl oder eine Gruppe der Formel -[X,]k-H, besonders bevorzugt sind R1 und R2 unabhängig voneinander Wasserstoff, Ci-C4-AIkVl, Cs-Cβ-Cycloalkyl oder eine Gruppe der Formel -[X,]k-H und ganz besonders bevorzugt Wasserstoff, Ci-C4-AIkVl, oder eine Gruppe der Formel -[X,]k-H. Insbesondere ist einer der Reste R1 und R2 Wasserstoff und der andere Ci-C4-Alkyl, oder eine Gruppe der Formel -[X,]k-H.Preferably, R 1 and R 2 are independently hydrogen, Ci-Ci 2 alkyl, Cs-Cβ-cycloalkyl or a group of the formula - [X,] kH, more preferably R 1 and R 2 are independently hydrogen, Ci-C 4 -AlkVl, Cs-Cβ-cycloalkyl or a group of the formula - [X,] kH and most preferably hydrogen, Ci-C 4 -AlkVl, or a group of the formula - [X,] kH. In particular, one of the radicals R 1 and R 2 is hydrogen and the other C 1 -C 4 -alkyl, or a group of the formula - [X,] kH.
Bevorzugte X, sind -CH2-CH2-O-, -CH2-CH2-N(H)-, -CH2-CH2-CH2-N(H)-, -CH2-CH(NH2)-, -CH2-CH(NHCHO)-, -CH2-CH(CHs)-O- und -CH(CHs)-CH2-O-, besonders bevorzugt ist -CH2-CH2-O-, -CH2-CH2-N(H)-, -CH2-CH2-CH2-N(H)- und -CH2-CH(NH2)-, ganz besonders bevorzugt ist -CH2-CH2-O-, -CH2-CH2-N(H)- und -CH2-CH2-CH2-N(H)-.
k ist bevorzugt 1 bis 30, besonders bevorzugt 1 bis 20, ganz besonders bevorzugt 1 bis 10 und insbesondere 1 bis 5.Preferred X, are -CH 2 -CH 2 -O-, -CH 2 -CH 2 -N (H) -, -CH 2 -CH 2 -CH 2 -N (H) -, -CH 2 -CH (NH 2 ) -, -CH 2 -CH (NHCHO) -, -CH 2 -CH (CHs) -O- and -CH (CHs) -CH 2 -O-, more preferably -CH 2 -CH 2 -O- , -CH 2 -CH 2 -N (H) -, -CH 2 -CH 2 -CH 2 -N (H) - and -CH 2 -CH (NH 2 ) -, very particularly preferably -CH 2 -CH 2 -O-, -CH 2 -CH 2 -N (H) - and -CH 2 -CH 2 -CH 2 -N (H) -. k is preferably 1 to 30, particularly preferably 1 to 20, very particularly preferably 1 to 10 and in particular 1 to 5.
Beispiele für R1 und/oder R2 sind Wasserstoff, Methyl, Ethyl, iso-Propyl, n-Propyl, n- Butyl, iso-Butyl, sek-Butyl, tert-Butyl, n-Hexyl, n-Heptyl, n-Octyl, n-Decyl, n-Dodecyl, n- Tetradecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl, 2-Ethylhexyl, Cyclopentyl, Cyclohe- xyl, Cyclooctyl, Cyclododecyl, 2-Hydroxyethyl, 2-Hydroxypropyl, 1-Hydroxypropyl, 5- Hydroxy-3-oxa-pentyl, 8-Hydroxy-3,6-dioxa-octyl oder 1 1-Hydroxy-3,6,9-trioxa-undecyl.Examples of R 1 and / or R 2 are hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-butyl Octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 2-hydroxyethyl, 2-hydroxypropyl, 1 Hydroxypropyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa-octyl or 1 1-hydroxy-3,6,9-trioxa-undecyl.
Y ist bevorzugt C2-Cio-Alkylen, besonders bevorzugt C2-C6-Alkylen, ganz besonders bevorzugt C2-C4-Alkylen, insbesondere C2-C3-Alkylen und speziell C2-Alkylen, wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiert sein können.Y is preferably C 2 -C 10 -alkylene, particularly preferably C 2 -C 6 -alkylene, very particularly preferably C 2 -C 4 -alkylene, in particular C 2 -C 3 -alkylene and especially C 2 -C 4 -alkylene, where the radicals mentioned are in each case represented by aryl, alkyl, aryloxy, Alkyloxy, heteroatoms and / or heterocycles can be substituted.
Beispiele für Y sind 1 ,2-Ethylen, 1 ,2-Propylen, 1 ,1-Dimethyl-1 ,2-ethylen, 1-Examples of Y are 1, 2-ethylene, 1, 2-propylene, 1, 1-dimethyl-1, 2-ethylene, 1
Hydroxymethyl-1 ,2-ethylen, 2-Hydroxy-1 ,3-propylen, 1 ,3-Propylen, 1 ,4-Butylen, 1 ,6- Hexylen, 2-Methyl-1 ,3-Propylen, 2-Ethyl-1 ,3-Propylen, 2,2-Dimethyl-1 ,3-Propylen und 2,2-Dimethyl-1 ,4-butylen, bevorzugt sind 1 ,2-Ethylen, 1 ,2-Propylen, 1 ,3-Propylen, besonders bevorzugt sind 1 ,2-Ethylen und 1 ,2-Propylen und ganz besonders bevorzugt ist 1 ,2-Ethylen.Hydroxymethyl-1,2-ethylene, 2-hydroxy-1,3-propylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl- 1, 3-propylene, 2,2-dimethyl-1,3-propylene and 2,2-dimethyl-1,4-butylene, preferred are 1,2-ethylene, 1,2-propylene, 1,3-propylene, Particular preference is given to 1,2-ethylene and 1,2-propylene and very particular preference to 1,2-ethylene.
Beispielhafte Amine sind Ammoniak, Methylamin, Dimethylamin, Ethylamin, Diethyla- min, iso-Propylamin, Di-iso-Propylamin, n-Butylamin, Di-n-Butylamin, tert-Butylamin, Monoethanolamin, Diethanolamin, Propanolamin, Dipropanolamin, Piperidin, Piperazin, Pyrrolidin, Cyclopentylamin, Cyclohexylamin, Anilin, Ethylendiamin, Diethylentriamin, Triethylentetramin, Tertraethylenpentamin und Polymere mit Aminfunktion wie in WO 04/050888 A1 auf der Seite 5, ab Zeile 28 bis Seite 6, Zeile 33 beschrieben.Exemplary amines are ammonia, methylamine, dimethylamine, ethylamine, diethylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tert-butylamine, monoethanolamine, diethanolamine, propanolamine, dipropanolamine, piperidine, piperazine , Pyrrolidine, cyclopentylamine, cyclohexylamine, aniline, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polymers with amine function as described in WO 04/050888 A1 on page 5, from line 28 to page 6, line 33.
Beispielhafte Carbonate sind Ethylencarbonat, 1 ,3-Propylencarbonat und 1 ,2- Propylencarbonat.Exemplary carbonates are ethylene carbonate, 1, 3-propylene carbonate and 1, 2-propylene carbonate.
Bevorzugte urethangruppenhaltige Alkohole (A) sind solche Verbindungen wie sie in der deutschen Offenlegungsschrift DE 10 2005 016 225 A1 offenbart sind. Von den darin genannten binären Gemischen von strukturisomeren ß-Hydroxyalkylcarabamten ist insbesondere das Isomerengemisch von Hydroxypropylcarbamat für das erfindungsgemäße Verfahren bevorzugt. Hydroxypropylcarbamat wird durch Umsetzung von 1 ,2-Propylencarbonat mit Ammoniak gemäß DE 10 2005 016 255 A1 erhalten.Preferred urethane group-containing alcohols (A) are those compounds as disclosed in German Offenlegungsschrift DE 10 2005 016 225 A1. Of the binary mixtures of structurallyomeric β-hydroxyalkylcarabamates mentioned therein, the isomer mixture of hydroxypropyl carbamate is particularly preferred for the process according to the invention. Hydroxypropylcarbamate is obtained by reacting 1, 2-propylene carbonate with ammonia according to DE 10 2005 016 255 A1.
Die Umsetzung des Amins mit dem Carbonat ist an sich bekannt, beispielsweise aus US 4,820,830 B, Spalte 4, Zeile 44 bis Spalte 5, Zeile 9, und nicht beschränkt.
Typischerweise werden das Amin und das Carbonat in einer Stöchiometrie von 0,7 bis 1 ,2 mol Amin : 1 mol Carbonat, bevorzugt 0,8 - 1 ,2 : 1 , besonders bevorzugt 0,9 - 1 ,1 :1 , ganz besonders bevorzugt 0,95 - 1 ,1 :1 und insbesondere 1 :1 mol/mol miteinander umgesetzt. Die Umsetzung erfolgt in der Regel bei einer Temperatur von 0 bis 120 0C, besonders bei 20 bis 100, ganz besonders bevorzugt 30 bis 80 und ganz besonders bevorzugt 40 bis 80 0C. Die Umsetzung ist in der Regel innerhalb von 12 Stunden beendet, bevorzugt innerhalb von 15 Minuten bis 10 Stunden, besonders bevorzugt in 30 Minuten bis 8 Stunden, ganz besonders bevorzugt 45 Minuten bis 6 Stunden und insbesondere innerhalb von 1 bis 4 Stunden.The reaction of the amine with the carbonate is known per se, for example from US 4,820,830 B, column 4, line 44 to column 5, line 9, and not limited. Typically, the amine and the carbonate in a stoichiometry of 0.7 to 1.2 moles of amine: 1 mol of carbonate, preferably 0.8 to 1, 2: 1, more preferably 0.9 to 1, 1: 1, very particularly preferably 0.95 - 1, 1: 1 and in particular 1: 1 mol / mol reacted with each other. The reaction is generally carried out at a temperature of from 0 to 120 ° C., especially from 20 to 100, very particularly preferably from 30 to 80 and very particularly preferably from 40 to 80 ° C. The reaction is generally completed within 12 hours, preferably within 15 minutes to 10 hours, more preferably in 30 minutes to 8 hours, most preferably 45 minutes to 6 hours, and especially within 1 to 4 hours.
Die Gesamtaminzahl gem. DIN 53176 des urethangruppenhaltigen Alkohols (A) sollte nicht mehr als 200 mg KOH/g betragen, vorzugsweise nicht mehr als 100 und ganz besonders bevorzugt nicht mehr als 80 mg KOH/g.The total amine number acc. DIN 53176 of the urethane group-containing alcohol (A) should not be more than 200 mg KOH / g, preferably not more than 100 and most preferably not more than 80 mg KOH / g.
Die Umsetzung des Amins mit dem Carbonat kann ohne Lösungsmittel durchgeführt werden oder in Anwesenheit eines solchen, beispielsweise Alkohole, Ether, Ketone, Kohlenwasserstoffe oder Wasser, bevorzugt ohne Lösungsmittel.The reaction of the amine with the carbonate can be carried out without solvent or in the presence of such, for example, alcohols, ethers, ketones, hydrocarbons or water, preferably without solvent.
Der urethangruppenhaltige Alkohol (A) kann in einem weiteren Schritt falls gewünscht aufgereinigt werden, beispielsweise durch Filtration, Destillation, Rektifikation, Chromatographie, Behandlung mit lonentauschern, Adsorbentien, neutraler, saurer und/oder alkalischer Wäsche, Strippen oder Kristallisation.If desired, the urethane group-containing alcohol (A) can be purified in a further step, for example by filtration, distillation, rectification, chromatography, treatment with ion exchangers, adsorbents, neutral, acidic and / or alkaline washing, stripping or crystallization.
In dem erfindungsgemäßen Verfahren kann der urethangruppenhaltige Alkohol (A) aufgereinigt eingesetzt werden. Dazu wird der urethangruppenhaltige Alkohol (A) kontinuierlich durch eine Reindestillation von leicht- und schwersiedenden Nebenkomponenten abgetrennt. Bei den leichtersiedenden Komponenten handelt es sich beispielsweise um nicht umgesetztes Carbonat oder um die korrespondierenden Diole. Als Schwersieder kommen höhermolekulare Nebenkomponenten in Betracht, die für die Farbgebung verantwortlich sind. Die Reindestillation erfolgt kontinuierlich im Feinvakuumbereich, d.h. bei einem verminderten Druck von 1 bis 100 mbar, bevorzugt 1 bis 50 mbar, besonders bevorzugt 1 bis 20 mbar und insbesondere im Bereich von 1 bis 10 mbar. Die Temperatur bei der Reindestillation liegt üblicherweise im Bereich von 50 bis 200 0C, bevorzugt im Bereich von 75 bis 180 0C und besonders bevorzugt im Be- reich von 100 bis 160 0C. Aufgrund der kurzen Verweilzeiten und der relativ geringen thermischen Belastung ist im Vergleich zur diskontinuierlichen Destillation ein hochreiner urethangruppenhaltiger Alkohol (A) erzielbar.In the method according to the invention, the urethane group-containing alcohol (A) can be used purified. For this purpose, the urethane-containing alcohol (A) is continuously separated by a pure distillation of low-boiling and high-boiling secondary components. The lower-boiling components are, for example, unreacted carbonate or the corresponding diols. As high boilers are higher molecular weight secondary components into consideration, which are responsible for the color. The purifying distillation is carried out continuously in the fine vacuum range, ie at a reduced pressure of 1 to 100 mbar, preferably 1 to 50 mbar, more preferably 1 to 20 mbar and in particular in the range of 1 to 10 mbar. The temperature in the purification by distillation is usually in the range of 50 to 200 0 C, preferably in the range of 75 to 180 0C, and particularly preferably in the range of 100 to 160 0 C. is due to the short residence times and relatively low thermal load Compared to the discontinuous distillation, a highly pure urethane group-containing alcohol (A) achievable.
(Meth)acrylsäureester eines gesättigten Alkohol (G) sind bevorzugt solche Ester von (Meth)acrylsäure mit einem gesättigten Ci-Cio-Alkohol.(Meth) acrylic esters of a saturated alcohol (G) are preferably those esters of (meth) acrylic acid with a saturated Ci-Cio-alcohol.
Beispiele für Verbindungen (G) sind (Meth)acrylsäuremethyl-, -ethyl-, -n-butyl-, -iso-
butyl-, n-octyl- und -2-Ethylhexylester, 1 ,2-Ethylenglycoldi- und -mono(meth)acrylat, 1 ,4-Butandioldi- und -mono(meth)acrylat, 1 ,6-Hexandioldi- und -mono(meth)acrylat, Trimethylolpropantri(meth)acrylat und Pentaerythrittetra(meth)acrylat.Examples of compounds (G) are (meth) acrylic acid methyl, -ethyl, -n-butyl, -iso- butyl, n-octyl and 2-ethylhexyl ester, 1, 2-ethylene glycol di- and mono (meth) acrylate, 1, 4-butanediol di- and mono (meth) acrylate, 1, 6-hexanediol di- and mono (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate.
Besonders bevorzugt sind (Meth)acrylsäuremethyl-, -ethyl-, -n-butyl- und -2-Particularly preferred are (meth) acrylic acid methyl, -ethyl, -n-butyl and -2-
Ethylhexylester und ganz besonders bevorzugt (Meth)acrylsäuremethyl-, -ethyl- und -n- butylester.Ethylhexylester and most preferably (meth) acrylic acid methyl, ethyl and n-butyl ester.
Erfindungsgemäß einsetzbare Enzyme (E) sind beispielsweise ausgewählt unter Hydrolasen, Esterasen (E.C. 3.1.-.-), Lipasen (E.C. 3.1.1.3), Glykosylasen (E.C. 3.2.-.-) und Proteasen (E.C. 3.4.-.-) in freier oder auf einem Träger chemisch oder physikalisch immobilisierter Form, bevorzugt Lipasen, Esterasen oder Proteasen. Besonders bevorzugt sind Novozym® 435 (Lipase aus Candida antartica B) oder Lipase aus Aspergillus sp., Aspergillus niger sp., Mucor sp., Penicilium cyclopium sp., Geotricum candidum sp., Rhizopus javanicus, Burholderia sp., Candida sp., Pseudomonas sp., oderEnzymes (E) which can be used according to the invention are selected, for example, from hydrolases, esterases (EC 3.1.-.-), lipases (EC 3.1.1.3), glycosylases (EC 3.2.-.-) and proteases (EC 3.4.-.-) in free or immobilized on a carrier chemically or physically immobilized form, preferably lipases, esterases or proteases. Particularly preferred Novozym ® 435 (lipase from Candida antartica B) or lipase from Aspergillus sp., Aspergillus niger sp., Mucor sp., Penicillium cyclopium sp., Geotricum candidum sp., Rhizopus javanicus, Burkholderia sp., Candida sp are., Pseudomonas sp., Or
Schweinepankreas, ganz besonders bevorzugt sind Lipase aus Candida antartica B oder aus Burholderia sp.Porcine pancreas, very particularly preferred are lipase from Candida antartica B or from Burholderia sp.
Erfindungswesentlich ist bei dem Verfahren, dass die Umesterung des (Meth)acrylsäureesters eines gesättigten Alkohols (G) mit einem urethangruppenhalti- gen Alkohol (A) mit einem Enzym (E) als Katalysator kontinuierlich erfolgt, wobei der (Meth)acryläureester eines gesättigten Alkohols (G) und der urethangruppenhaltigen Alkohol (A) kontinuierlich über mindestens einen Festbettreaktor gefüllt mit einem immobilisierten Enzym (E) als Katalysator geleitet werden.It is essential to the process according to the invention that the transesterification of the (meth) acrylic acid ester of a saturated alcohol (G) with a urethane group-containing alcohol (A) with an enzyme (E) as catalyst takes place continuously, the (meth) acrylic acid ester of a saturated alcohol ( G) and the urethane group-containing alcohol (A) are continuously passed through at least one fixed bed reactor filled with an immobilized enzyme (E) as a catalyst.
Dabei kann der (Meth)acrylsäureester des gesättigten Alkohols (G) mit dem urethangruppenhaltigen Alkohol (A) zuvor miteinander vermischt werden, und diese Reaktionsmischung wird anschließend über den mindestens einen Festbettreaktor gefüllt mit einem immobilisierten Enzym (E) geleitet. Die Reaktanden können auch getrennt von- einander gleichzeitig über das immobiliserte Enzym (E) geleitet werden. Bevorzugt wird zunächst eine Reaktionsmischung aus (Meth)acrylsäureester (G) und urethangruppen- haltiger Alkohol (A) hergestellt, die anschließend über das immobilisierte Enzym (E) geleitet wird.In this case, the (meth) acrylic ester of the saturated alcohol (G) with the urethane group-containing alcohol (A) are previously mixed together, and this reaction mixture is then passed through the at least one fixed bed reactor filled with an immobilized enzyme (E). The reactants can also be passed separately from one another simultaneously via the immobilized enzyme (E). Preferably, a reaction mixture of (meth) acrylic acid ester (G) and urethane group-containing alcohol (A) is first prepared, which is then passed over the immobilized enzyme (E).
Das molare Verhältnis von (Meth)acrylsäureester eines gesättigten Alkohols (G) (bezogen auf die (Meth)acryleinheiten) zu urethangruppenhaltigem Alkohol (A) (bezogen auf Hydroxygruppen) kann in einem weiten Bereich, wie z.B. im Verhältnis 100:1 bis 1 :1 , bevorzugt 50:1 bis 1 :1 , besonders bevorzugt 20:1 bis 1 :1 und ganz besonders bevorzugt 10:1 bis 1 :1 , schwanken.The molar ratio of (meth) acrylic ester of a saturated alcohol (G) (based on the (meth) acrylic units) to urethane group-containing alcohol (A) (relative to hydroxy groups) can be varied over a wide range, e.g. in the ratio 100: 1 to 1: 1, preferably 50: 1 to 1: 1, more preferably 20: 1 to 1: 1 and most preferably 10: 1 to 1: 1, vary.
Das Enzym (E) ist in dem erfindungsgemäßen Verfahren auf einem geeigneten Träger immobilisiert. Dabei existieren fünf klassische Methoden der Immobilisierung von En-
zymen, nämlich die Adsorption, die kovalente Bindung, der Membraneinschluß, der Geleinschluß und die Quervernetzung. Dabei können unterschiedliche Trägermaterialien eingesetzt werden, wobei die chemischen Wechselwirkungen der Trägeroberfläche mit dem Enzym so angepasst sein müssen, dass keine unerwünschten Nebenwirkun- gen, wie z.B. Inaktivierung entstehen. Als feste Träger eignen sich prinzipiell verschiedene anorganische und organische Materialien, letztere können natürlichen oder synthetischen Ursprungs sein. Anorganische Träger weisen meistens eine hohe Druckstabilität auf, während organische Träger eine gute chemische Stabilität zeigen. Als anorganische Träger werden überwiegend poröse Materialien auf der Basis von Silicium- oder Aluminumoxiden bzw. Gemischen daraus eingesetzt. Natürliche organische Träger sind beispielsweise Polysaccharide wie z.B. Cellulose, Stärke, Dextran, Agarose und Chitin. Aber auch Proteine wie Kollagen, Gelatine und Albumin kommen zur Anwendung. Als synthetische organische Polymere dienen Poly(meth)acrylate, Polyacrylamide, Vinyl- und Allylpolymere, Polyester oder Polyamide.The enzyme (E) is immobilized on a suitable support in the method according to the invention. There are five classical methods of immobilizing enzymes, namely adsorption, covalent bonding, membrane entrapment, gel entrapment and cross-linking. In this case, different carrier materials can be used, wherein the chemical interactions of the carrier surface with the enzyme must be adjusted so that no unwanted side effects, such as inactivation occur. In principle, various inorganic and organic materials are suitable as solid carriers, the latter being of natural or synthetic origin. Inorganic carriers usually have high pressure stability, while organic carriers show good chemical stability. The inorganic carriers used are predominantly porous materials based on silicon or aluminum oxides or mixtures thereof. Natural organic carriers are, for example, polysaccharides such as cellulose, starch, dextran, agarose and chitin. But also proteins like collagen, gelatine and albumin are used. Synthetic organic polymers are poly (meth) acrylates, polyacrylamides, vinyl and allyl polymers, polyesters or polyamides.
Bevorzugt werden in dem erfindungsgemäßen Verfahren Enzyme eingesetzt, die bereits auf einem geeigneten Träger immobilisiert sind. Derartige immobilisierte Enzyme, bevorzugt Lipasen, sind unter dem Handelsnamen Novozym® 435 (Lipase aus Candida antartica B) von der Firma Novozymes erhältlich.In the process according to the invention, preference is given to using enzymes which are already immobilized on a suitable support. Such immobilized enzymes, preferably lipases, under the trade name Novozym ® 435 (lipase from Candida antartica B) are available from the company Novozymes.
Das immobilisierte Enzym wird in einer als Festbettreaktor geeigneten Vorrichtung, beispielsweise einem Rohr oder einer Säule, bereitgestellt. Anschließend werden die Reaktanden oder bevorzugt die vorgemischte Reaktionsmischung aus einem (Meth)acrylsäureester (G) und einem urethangruppenhaltigen Alkohol (A) mit Hilfe ei- ner Pumpe über den mit dem immobiliserten Enzym beschickten Festbettreaktor gepumpt.The immobilized enzyme is provided in a device suitable as a fixed bed reactor, for example a tube or a column. Subsequently, the reactants or preferably the premixed reaction mixture of a (meth) acrylic acid ester (G) and a urethane group-containing alcohol (A) are pumped by means of a pump over the fixed bed reactor charged with the immobilized enzyme.
Die enzymatische Umesterung mit einem (Meth)acryläsureester eines gesättigten Alkohols (G) erfolgt im Allgemeinen bei 0 bis 100 0C, bevorzugt 20 bis 80 0C, besonders bevorzugt 20 bis 700C, ganz besonders bevorzugt 20 bis 60 0C.The enzymatic transesterification with a (meth) acrylic ester of a saturated alcohol (G) is generally carried out at 0 to 100 0 C, preferably 20 to 80 0 C, more preferably 20 to 70 0 C, most preferably 20 to 60 0 C.
Die Reaktion kann in organischen Lösungsmitteln oder deren Gemischen oder ohne Zusatz von Lösungsmitteln ablaufen. Die Ansätze sind in der Regel weitgehend wasserfrei (d.h. unter 10, bevorzugt unter 5, besonders bevorzugt unter 1 Vol.- % Wasser- zusatz).The reaction can take place in organic solvents or mixtures thereof or without the addition of solvents. The batches are generally largely anhydrous (i.e., below 10, preferably below 5, more preferably below 1% by volume of water additive).
Der Anteil organischer Lösungsmittel beträgt beispielsweise 0,01-30 Gew.-%, bevorzugt 0,1-5 Gew.-%. Geeignete organische Lösungsmittel sind solche für diese Zwecke bekannten, beispielsweise tertiäre Monoole, wie Cs-Cβ-Alkohole, bevorzugt tert- Butanol, tert-Amylalkohol, Pyridin, Poly-Ci-C4-alkylenglykoldi-Ci-C4-alkylether, bevorzugt Polyethylenglycoldi-Ci-C4-alkylether, wie z.B. 1 ,2-Dimethoxyeethan, Diethylengly- coldimethylether, Polyethylenglycoldimethylether 500, Ci-C4-Alkylencarbonate, insbe-
sondere Propylencarbonat, Cs-Cβ-Alkylessigsäureester, insbesondere tert.-Butyl- essigsäureester, THF, Toluol, 1 ,3-Dioxolan, Aceton, iso-Butyl-methylketon, Ethylme- thylketon, 1 ,4-Dioxan, tert-Butylmethylether, Cyclohexan, Methylcyclohexan, Toluol, Hexan, Dimethoxymethan, 1 ,1-Dimethoxyethan, Acetonitril, sowie deren ein- oder mehrphasige Mischungen.The proportion of organic solvents is for example 0.01-30 wt .-%, preferably 0.1-5 wt .-%. Suitable organic solvents are known for this purpose, for example tertiary monools, such as Cs-Cβ alcohols, preferably tert-butanol, tert-amyl alcohol, pyridine, poly-Ci-C4-alkylenglykoldi-Ci-C4-alkyl ethers, preferably Polyethylenglycoldi-Ci C 4 -alkyl ethers, such as, for example, 1, 2-dimethoxyethane, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether 500, C 1 -C 4 -alkylene carbonates, in particular in particular propylene carbonate, Cs-Cβ-alkylacetic acid esters, in particular tert-butylacetic acid esters, THF, toluene, 1,3-dioxolane, acetone, isobutyl methyl ketone, ethyl methyl ketone, 1,4-dioxane, tert-butyl methyl ether, cyclohexane , Methylcyclohexane, toluene, hexane, dimethoxymethane, 1, 1-dimethoxyethane, acetonitrile, as well as their mono- or multiphase mixtures.
Wahlweise können zu den organischen Lösungsmitteln wässrige Lösungsmittel zugesetzt werden, so dass - je nach organischem Lösungsmittel - ein- oder mehrphasige Reaktionslösungen entstehen. Beispiele für wässrige Lösungsmittel sind Wasser sowie wässrige, verdünnte (z.B. 10 bis 100 mM) Puffer, beispielsweise mit einem pH-Wert im Bereich von etwa 6 bis 8, wie z.B. Kaliumphosphat- oder TRIS-HCI-Puffer.Optionally, aqueous solvents can be added to the organic solvents, so that - depending on the organic solvent - single- or multi-phase reaction solutions. Examples of aqueous solvents are water as well as aqueous, dilute (e.g., 10 to 100 mM) buffers, for example, having a pH in the range of about 6 to 8, e.g. Potassium phosphate or TRIS-HCl buffer.
Der Wasseranteil im Reaktionsansatz liegt in der Regel bei 0-10 Vol%. Bevorzugt werden die Reaktanden ohne Vorbehandlung (Trocknung, Wasserdotierung) eingesetzt.The proportion of water in the reaction mixture is usually 0-10% by volume. The reactants are preferably used without pretreatment (drying, water doping).
Bevorzugt wird die enzymatische Umesterung ohne Zusatz von Wasser und organischen Lösungsmitteln durchgeführt.Preferably, the enzymatic transesterification is carried out without the addition of water and organic solvents.
Erfindungsgemäß wird die Reaktion kontinuierlich über mindestens einen Festbettreak- tor gefüllt mit einem immobiliserten Enzym (E) durchgeführt. Dazu werden aus einem Vorlagegefäß die Reaktanden oder die vorgemischte Reaktionsmischung mit Hilfe einer Pumpe über den mit dem immobilisierten Enzym beschickten Festbettreaktor gepumpt. Das dabei entstehende Rohprodukt enthaltend den urethangruppenhaltigen (Meth)acrylsäureester (U) wird in einem geeigneten Vorratsgefäß gesammelt.According to the invention, the reaction is carried out continuously via at least one fixed bed reactor filled with an immobilized enzyme (E). For this purpose, the reactants or the premixed reaction mixture are pumped from a receiver vessel by means of a pump over the fixed bed reactor charged with the immobilized enzyme. The resulting crude product containing the urethane group-containing (meth) acrylic ester (U) is collected in a suitable storage vessel.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird das Rohprodukt zunächst destillativ gereinigt, wobei über eine angeschlossene Destillationskolonne das Azeotrop aus freiwerdendem gesättigten Alkohol und überschüssigem korrespondierendem (Meth)acrylsäureester (G) und gegebenenfalls verwendetem Schleppmittel abgetrennt wird.In a preferred embodiment of the process according to the invention, the crude product is first purified by distillation, the azeotrope being freed from saturated saturated alcohol and excess corresponding (meth) acrylic ester (G) and optionally used entrainer via a connected distillation column.
Gegebenenfalls wird zusätzlich ein Schleppmittel eingesetzt, das mit dem freiwerdenden gesättigten Alkohol und dem damit überschüssigen korrespondierenden (Meth)acrylsäureester (G) ein Azeotrop bildet. Bevorzugt handelt es sich um ein Schleppmittel, dessen mit dem freiwerdenden gesättigten Alkohol und dem damit überschüssigen korrespondierenden (Meth)acrylsäureester (G) gebildetes Azeotrop einen Phasenzerfall zeigt oder welches durch Wasserzugabe gebrochen werden kann. Solche geeigneten Schleppmittel sind beispielsweise n-Pentan, n-Hexan, n-Heptan, Cyclohexan, Methylcyclohexan, Benzol, Toluol, XyIoI und beliebige Mischungen davon.Optionally, an additional entrainer is used which forms an azeotrope with the liberated saturated alcohol and the excess of corresponding (meth) acrylic acid ester (G). It is preferably an entraining agent whose azeotrope formed with the saturated alcohol liberated and the excess corresponding corresponding (meth) acrylic ester (G) shows a phase decay or which can be broken by addition of water. Such suitable entrainers are, for example, n-pentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and any mixtures thereof.
Die für die Abtrennung des Azeotrops verwendete Destillationskolonne ist von an sich bekannter Bauart und weist die üblichen Einbauten auf. Als Kolonneneinbauten kom-
men prinzipiell alle gängigen Einbauten in Betracht, beispielsweise Böden, Packungen und/oder Schüttungen. Von den Böden sind Glockenböden, Siebböden, Ventilböden, Thormannböden und/oder Dual/Flow-Böden bevorzugt, von den Schüttungen sind solche mit Ringen, Wendeln, Sattelkörpern oder Geflechten bevorzugt. In der Regel sind 5 bis 20 theoretische Böden ausreichend.The distillation column used for the separation of the azeotrope is of a known type and has the usual internals. As column internals men in principle all common installations into consideration, for example, soils, packings and / or beds. Of the soils, bubble-cap trays, sieve trays, valve trays, Thormann trays and / or dual / flow trays are preferred; of the trays, those with rings, spirals, saddles or braids are preferred. As a rule, 5 to 20 theoretical plates are sufficient.
Das abdestillierte Azeotrop wird anschließend in einem Kondensator herkömmlicher Bauart kondensiert.The distilled azeotrope is then condensed in a condenser of conventional design.
Das auf diese Weise gereinigte Produkt enthaltend den urethangruppenhaltigenThe product purified in this way containing the urethane group-containing
(Meth)acrylsäureester (U) wird anschließend einem zweiten, mit immobilisiertem Enzym (E) beschickten Festbettreaktor zugeführt und mit Hilfe einer Pumpe über diesen Festbettreaktor gepumpt. In einem angeschlossenen Vorratsgefäß wird das Endprodukt gesammelt.(Meth) acrylic ester (U) is then fed to a second, with immobilized enzyme (E) fed fixed bed reactor and pumped by means of a pump through this fixed bed reactor. The final product is collected in a connected storage vessel.
Die Leistung der Pumpe, mit der die Reaktionsmischung über die mit immobilisierten Enzym beschickten Festbettreaktoren gepumpt wird, wird so eingestellt, dass am Aus- lass des Enzymfestbetts der thermodynamische Gleichgewichtszustand erreicht wird.The capacity of the pump to pump the reaction mixture over the fixed bed reactors charged with immobilized enzyme is adjusted to achieve the thermodynamic equilibrium state at the outlet of the enzyme fixed bed.
Optional ist es in einer anderen Ausführungsform des erfindungsgemäßen Verfahrens möglich, dass der urethangruppenhaltige (Meth)acrylsäureester nach Verlassen des mindestens einen mit immobilisierten Enzym (E) beschickten Festbettreaktors und vor dem Auffangen im Vorratsgefäß einem Extraktionsvorgang unterzogen wird.Optionally, in another embodiment of the method according to the invention, it is possible that the urethane group-containing (meth) acrylic acid ester is subjected to an extraction process after leaving the at least one fixed bed reactor charged with immobilized enzyme (E) and before collecting in the storage vessel.
Die Extraktion erfolgt üblicherweise mit Wasser, wobei der restliche urethangruppenhaltige Alkohol (A) in die wässrige Phase übergeht und somit vom Endprodukt abgetrennt wird. Die organische Phase enthaltend urethangruppenhaltigen (Meth)acrylsäureester (U) und gegebenenfalls noch restlichen (Meth)acrylsäureester (G) kann in einer zuvor beschriebenen Destillationskolonne aufgereinigt werden, wobei der (Meth)acrylsäureester (G) als Leichtsieder vom Endprodukt abgetrennt wird.The extraction is usually carried out with water, wherein the remaining urethane group-containing alcohol (A) passes into the aqueous phase and is thus separated from the final product. The organic phase containing urethane group-containing (meth) acrylic acid ester (U) and optionally remaining (meth) acrylic acid ester (G) can be purified in a previously described distillation column, wherein the (meth) acrylic acid ester (G) is separated as low boilers from the final product.
Falls Lösungsmittel eingesetzt werden, erfolgt die Abtrennung vom organischen Lösungsmittel in der Regel durch Destillation, Rektifikation oder bei festen Reaktionsprodukten durch Filtration.If solvents are used, the separation from the organic solvent is usually carried out by distillation, rectification or in the case of solid reaction products by filtration.
Zur weiteren Aufreinigung des Reaktionsproduktes kann auch eine Chromatographie oder eine Reindestillation durchgeführt werden.For further purification of the reaction product, a chromatography or a purifying distillation can also be carried out.
Falls eine Reindestillation zur Aufreinigung des Reaktionsproduktes durchgeführt wird, wird aus dem unter der gegebenenfalls erfolgten Lösungsmitteldestillation anfallenden Sumpf der urethangruppenhaltige (Meth)acrylsäureester (U) in einem weiteren Destillationsschritt als Kopfprodukt isoliert und mit mindestens einem der unten genannten
Polymerisationsinhibitoren stabilisiert. Von den dort genannten Stabilisatoren sind für die Reindestillation insbesondere Hydrochinonmonomethylether und Phenothiazin geeignet.If a purifying distillation is carried out for the purification of the reaction product, the urethane group-containing (meth) acrylic ester (U) is isolated from the bottom obtained from the solvent distillation, if appropriate, in a further distillation step as top product and with at least one of the below Stabilized polymerization inhibitors. Of the stabilizers mentioned there, hydroquinone monomethyl ether and phenothiazine are particularly suitable for the purifying distillation.
Die für diesen Destillationsschritt verwendbare Rektifikationskolonne ist von bekannter Bauart, wie beispielsweise Füllkörperkolonnen, Packungskolonnen oder Bodenkolonnen, und hat trennwirksame Einbauten (z.B. Glocken-, Sieb- oder Dual-Flow-Böden) oder enthält Schüttungen oder gerichtete Packungen. Diese üblichen Einbauten weisen bevorzugt 10 bis 20 theoretische Böden auf. Auch Dünnschichtverdampfer kom- men in Frage. Verdampfer und Kondensator sind ebenfalls herkömmlicher Bauart.The rectification column useful for this distillation step is of known type, such as packed columns, packed columns, or tray columns, and has separable internals (e.g., bell, sieve, or dual-flow trays) or contains beds or directional packing. These conventional internals preferably have 10 to 20 theoretical plates. Thin-film evaporators are also suitable. Evaporator and condenser are also conventional design.
Bevorzugt wird der urethangruppenhaltige (Meth)acrylsäureester (U) bei einer Sumpftemperatur von 100 - 1400C, bevorzugt von 110 - 1300C und einem Kopfdruck von 1 bis 100 mbar, bevorzugt von 1 bis 50 mbar, besonders bevorzugt von 1 bis 10 mbar und insbesondere von 1 bis 5 mbar erhalten.The urethane (meth) is preferably acrylate (U) at a bottom temperature from 100 to 140 0 C, preferably 110-130 0 C and a head pressure of 1 to 100 mbar, preferably from 1 to 50 mbar, particularly preferably from 1 to 10 mbar and in particular from 1 to 5 mbar.
Zur Stabilisierung kann in den Kondensator eine Lösung von 0,05 - 0,5% Hydrochinonmonomethylether oder ein anderer ähnlich wirksamer Lagerstabilisator eingesprüht werden, wobei die Menge so gewählt wird, dass das Kondensat eine Lagerstabilisator- konzentration von 10 - 20 ppm aufweist. Ein Teil des Kondensats, bevorzugt 10 - 20%, kann der Kolonne wieder als Rücklauf zugeführt werden.For stabilization, a solution of 0.05-0.5% hydroquinone monomethyl ether or another similarly effective storage stabilizer may be sprayed into the condenser, the amount being chosen such that the condensate has a storage stabilizer concentration of 10-20 ppm. A portion of the condensate, preferably 10-20%, can be returned to the column as reflux.
Der anfallende urethangruppenhaltige (Meth)acrylsäureester (U) hat entsprechend der gaschromatographischen Analyse eine Reinheit von mindestens 98,5%, bevorzugt mindestens 99,0% und besonders bevorzugt mindestens 99,5%.The resulting urethane group-containing (meth) acrylic ester (U) has, according to the gas chromatographic analysis, a purity of at least 98.5%, preferably at least 99.0% and particularly preferably at least 99.5%.
Das Sumpfprodukt der Reindestillation, das hauptsächlich aus restlichem urethangrup- penhaltigen (Meth)acrylsäureester (U), Michael-Additionsprodukten, Stabilisator und Polymeren besteht, kann in eine Rückstandsdestillation und/oder Rückstandsspaltung geleitet werden.The bottom product of the purifying distillation, which consists mainly of residual urethane (meth) acrylate (U), Michael addition products, stabilizer and polymers can be passed into a residue distillation and / or residue splitting.
Selbstverständlich ist es auch möglich, die Destillationseinheiten der gegebenenfalls erfolgten Lösungsmitteldestillation und die Reindestillation zu vereinigen. In diesem Fall wird der reine urethangruppenhaltige (Meth)acrylsäureester (U) über einen Seiten- abzug, bevorzugt gasförmig, im unteren Kolonnenbereich, bevorzugt in der unteren Hälfte, besonders bevorzugt im unteren Drittel, ausgeschleust, kondensiert und wie oben beschrieben stabilisiert.Of course, it is also possible to combine the distillation units of the solvent distillation, if appropriate, and the purifying distillation. In this case, the pure urethane group-containing (meth) acrylic acid ester (U) is discharged via a side draw, preferably gaseous, in the lower column region, preferably in the lower half, more preferably in the lower third, condensed and stabilized as described above.
Bevorzugt werden im Aufreinigungsschritt jedoch lediglich das eingesetzte Enzym und das gegebenenfalls eingesetzte Lösungsmittel abgetrennt.In the purification step, however, it is preferred to separate only the enzyme used and the solvent used if appropriate.
Die Reaktionsbedingungen bei der enzymatischen Umesterung sind mild. Aufgrund der
niedrigen Temperaturen und sonstigen milden Bedingungen wird die Bildung von Nebenprodukten bei der Umesterung vermieden, die andernfalls zum Beispiel von chemischen Katalysatoren stammen können oder durch unerwünschte radikalische Polymerisation des eingesetzten (Meth)acrylatsäureesters (G), die sonst nur durch Zugabe von Stabilisatoren verhindert werden kann.The reaction conditions in the enzymatic transesterification are mild. Due to the low temperatures and other mild conditions, the formation of by-products in the transesterification is avoided, which may otherwise be derived, for example, from chemical catalysts or by unwanted radical polymerization of the (meth) acrylates used (G), which can otherwise be prevented only by the addition of stabilizers ,
Da es sich bei dem in dem erfindungsgemäßen Verfahren eingesetzten (Meth)acrylsäureester eines gesättigten Alkohols (G) als auch bei dem urthangruppen- haltigen (Meth)acrylsäureester (U) um polymerisationsfähige Verbindungen handelt, ist in allen Verfahrensschritten auf eine ausreichende Polymerisationsinhibierung zu achten. Daher findet die Umesterung erfindungsgemäß in Gegenwart mindestens eines Polymerisationsinhibitors (P) statt. Dabei kann es sich um den ohnehin im (Meth)acrylsäureester (G) enthaltenen Lagerstabilisator handeln, es kann aber auch nich ein weiterer Polymerisationsinhibitor zugesetzt werden.Since the (meth) acrylic acid ester of a saturated alcohol (G) used in the process according to the invention and the (meth) acrylic acid ester (U) containing urethane groups are polymerizable compounds, adequate polymerization inhibition must be ensured in all process steps. Therefore, the transesterification according to the invention takes place in the presence of at least one polymerization inhibitor (P). This can be the storage stabilizer contained in the (meth) acrylic ester (G) anyway, but it is also not possible to add a further polymerization inhibitor.
In der Regel werden, bezogen auf die ungesättigten Monomere, je Einzelsubstanz vonIn general, based on the unsaturated monomers, each individual substance of
1 bis 10 000 ppm, bevorzugt von 10 bis 5 000 ppm, besonders bevorzugt von 30 bisFrom 1 to 10,000 ppm, preferably from 10 to 5,000 ppm, more preferably from 30 to
2 500 ppm und insbesondere von 50 bis 1 500 ppm eines geeigneten Polymerisationsinhibitors (P) eingesetzt.2,500 ppm and in particular from 50 to 1,500 ppm of a suitable polymerization inhibitor (P) used.
Geeignete Polymerisationsinhibitoren (P) können beispielsweise N-Oxide (Nitroxyl- oder N-Oxyl-Radikale, also Verbindungen, die wenigstens eine >N-0 -Gruppe aufweisen), wie z. B. 4-Hydroxy-2,2,6,6-tetramethylpiperidin-N-oxyl, 4-0x0-2,2,6,6- tetramethylpiperidin-N-oxyl, 4-Acetoxy-2,2,6,6-tetramethyl-piperidin-N-oxyl, 2,2,6,6- Tetramethylpiperidin-N-oxyl, 4,4',4"-Tris(2,2,6,6-tetramethyl-piperidin-N-oxyl)-phosphit oder 3-0x0-2,2, 5, 5-tetramethyl-pyrrolidin-N-oxyl; ein- oder mehrwertige Phenole, die ggf. eine oder mehrere Alkylgruppen aufweisen, wie z. B. Alkylphenole, beispielsweise o-, m- oder p-Kresol (Methylphenol), 2-tert.-Butylphenol, 4-tert.-Butylphenol, 2,4-Di- tert.-butylphenol, 2-Methyl-4-tert.-butylphenol, 2-tert.-Butyl-4-methylphenol, 2,6-tert- Butyl-4-methylphenol, 4-tert.-Butyl-2,6-dimethylphenol oder 6-tert.-Butyl-2,4- dimethylphenol; Chinone, wie z. B. Hydrochinon, Hydrochinonmonomethylether, 2- Methylhydrochinon oder 2,5-Di-tert.-Butylhydrochinon; Hydroxyphenole, wie beispielsweise Brenzcatechin (1 ,2-Dihydroxybenzol) oder Benzochinon; Aminophenole, wie z. B. p-Aminophenol; Nitrosophenole, wie z. B. p-Nitrosophenol; Alkoxyphenole, wie bei- spielsweise 2-Methoxyphenol (Guajacol, Brenzcatechinmonomethylether), 2-Suitable polymerization inhibitors (P) may for example be N-oxides (nitroxyl or N-oxyl radicals, ie compounds which have at least one> N-0 group), such as. 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-0x0-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2,2,6,6- tetramethyl-piperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4,4 ', 4 "-tris (2,2,6,6-tetramethyl-piperidine-N-oxyl) -phosphite or 3-0x0-2,2, 5, 5-tetramethylpyrrolidine-N-oxyl; mono- or polyhydric phenols which optionally have one or more alkyl groups, such as, for example, alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 2-tert-butyl 4-methylphenol, 2,6-tert-butyl-4-methylphenol, 4-tert-butyl-2,6-dimethylphenol or 6-tert-butyl-2,4-dimethylphenol; quinones such as hydroquinone Hydroquinone monomethyl ether, 2-methylhydroquinone or 2,5-di-tert-butylhydroquinone; hydroxyphenols such as catechol (1, 2-dihydroxybenzene) or benzoquinone; aminophenols such as p-aminophenol; nitrosophenols such as e.g. p-nitrosophenol; alkoxyphenols, such as for example for example 2-methoxyphenol (guaiacol, catechol monomethyl ether), 2-
Ethoxyphenol, 2-lsopropoxyphenol, 4-Methoxyphenol (Hydrochinonmonomethylether), Mono- oder Di-tert.-Butyl-4-methoxyphenol; Tocipherole, wie z. B. α-Tocopherol sowie 2,3-Dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-Dimethyl-7-hydroxycumaran), a- romatische Amine, wie z. B. N,N-Diphenylamin oder N-Nitroso-diphenylamin; Pheny- lendiamine, wie z. B. N,N'-Dialkyl-p-phenylendiamin, wobei die Alkylreste gleich oder verschieden sein können und jeweils unabhängig voneinander aus 1 bis 4 Kohlenstoffatomen bestehen und geradkettig oder verzweigt sein können, wie z. B. N,N'-Dimethyl-
p-phenylendiamin oder N,N'-Diethyl-p-phenylendiamin, Hydroxylamine, wie z.B. N, N- Diethylhydroxylamin, Imine, wie z. B. Methylethylimin oder Methylen violett, Sulfonamide, wie z. B. N-Methyl-4-toluolsulfonamid oder N-tert.-Butyl-4-toluolsulfonamid, Oxime, wie Aldoxime, Ketoxime oder Amidoxime, wie z. B. Diethylketoxim, Methylethylketoxim oder Salicyladoxim, phosphorhaltige Verbindungen, wie z. B. Triphenylphosphin,Ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl-4-methoxyphenol; Tocipherole, such as. B. α-tocopherol and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxy-coumaran), a- aromatic amines, such as. N, N-diphenylamine or N-nitroso-diphenylamine; Phenylenediamine, such as. B. N, N'-dialkyl-p-phenylenediamine, wherein the alkyl radicals may be the same or different and each independently consist of 1 to 4 carbon atoms and may be straight or branched, such as. N, N'-dimethyl p-phenylenediamine or N, N'-diethyl-p-phenylenediamine, hydroxylamines, such as N, N-diethylhydroxylamine, imines, such as. As methylethylimine or methylene violet, sulfonamides, such as. As N-methyl-4-toluenesulfonamide or N-tert-butyl-4-toluenesulfonamide, oximes, such as Aldoxime, Ketoxime or amidoximes, such as. B. diethyl ketoxime, methyl ethyl ketoxime or salicylic oxime, phosphorus-containing compounds such. B. triphenylphosphine,
Triphenylphosphit, Triethylphosphit, Hypophsophorige Säure oder Alkylester der Phosphorigen Säuren; schwefelhaltige Verbindungen wie z. B. Diphenylsulfid oder Phe- nothiazin; Metallsalze, wie Kupfer- oder Mangan-, Cer-, Nickel-, Chromsalze, beispielsweise -Chloride, -sulfate, -salicylate, -tosylate, -acrylate oder -acetate, wie z. B. Kupferacetat, Kupfer(ll)chlorid, Kupfersalicylat, Cer(lll)acetat oder Cer(lll)ethylhexanoat, oder Gemische davon sein.Triphenyl phosphite, triethyl phosphite, hypophosphorous acid or alkyl esters of phosphorous acids; sulfur compounds such. Diphenyl sulfide or phenothiazine; Metal salts such as copper or manganese, cerium, nickel, chromium salts, for example chlorides, sulfates, salicylates, tosylates, acrylates or acetates, such as. Copper acetate, copper (II) chloride, copper salicylate, cerium (III) acetate or cerium (III) ethylhexanoate, or mixtures thereof.
Bevorzugt wird als Polymerisationsinhibitor(gemisch) mindestens eine Verbindung aus der Gruppe Hydrochinon, Hydrochinonmonomethylether, Phenothiazin, 4-Hydroxy- 2,2,6,6-tetramethylpiperidin-N-oxyl, 4-Oxo-2,2, 6, 6-tetramethylpiperidin-N-oxyl, 2-tert- Butylphenol, 4-tert.-Butylphenol, 2,4-Di-tert.-Butylphenol, 2-tert.-Butyl-4-methylphenol, 6-tert.-Butyl-2,4-dimethylphenol, 2,6-Di-tert.-Butyl-4-methylphenol, 2-Methyl-4-tert.- butylphenol, Hypophosphorige Säure, Kupferacetat, Kupfer(ll)chlorid, Kupfersalicylat und Cer(lll)acetat.Preference is given as polymerization inhibitor (mixture) at least one compound from the group hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine N-oxyl, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4 -dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-methyl-4-tert-butylphenol, hypophosphorous acid, copper acetate, copper (II) chloride, copper salicylate and cerium (III) acetate.
Ganz besonders bevorzugt wird Phenothiazin und/oder Hydrochinonmonomethylether (MEHQ) als Polymerisationsinhibitor (P) verwendet.Very particular preference is given to using phenothiazine and / or hydroquinone monomethyl ether (MEHQ) as the polymerization inhibitor (P).
Zur weiteren Stützung der Stabilisierung wird bevorzugt ein sauerstoffhaltiges Gas, bevorzugt Luft oder ein Gemisch aus Luft und Stickstoff (Magerluft) anwesend sein.To further support the stabilization, an oxygen-containing gas, preferably air or a mixture of air and nitrogen (lean air) will preferably be present.
Durch das erfindungsgemäße Verfahren sind in einer bevorzugten Ausführungsform urethangruppenhaltige (Meth)acrylsäureester (U) der Formel (I) zugänglich,In a preferred embodiment, urethane group-containing (meth) acrylic esters (U) of the formula (I) are obtainable by the process according to the invention,
worin wherein
R1 und R2 die oben genannten Bedeutungen haben,R 1 and R 2 have the meanings given above,
Y ausgewählt ist unter 1 ,2-Ethylen, 1 ,2-Propylen, 1 ,1-Dimethyl-1 ,2-ethylen, 1-Y is selected from 1, 2-ethylene, 1, 2-propylene, 1, 1-dimethyl-1, 2-ethylene, 1
Hydroxy-methyl-1 ,2-ethylen, 2-Hydroxy-1 ,3-propylen, 2-Hydroxy-1 ,3-propylen, 1 ,3-Propylen, 1 ,4-Butylen, 1 ,6-Hexylen, 2-Methyl-1 ,3-Propylen, 2-Ethyl-1 ,3- Propylen, 2,2-Dimethyl-1 ,3-Propylen und 2,2-Dimethyl-1 ,4-butylen,
R3 Wasserstoff oder Methyl, bevorzugt Wasserstoff bedeutet, mit der Maßgabe, dass mindestens einer der Reste R1 und R2 ungleich Wasserstoff ist.Hydroxy-methyl-1,2-ethylene, 2-hydroxy-1,3-propylene, 2-hydroxy-1,3-propylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2- Methyl-1, 3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene and 2,2-dimethyl-1,4-butylene, R 3 is hydrogen or methyl, preferably hydrogen, with the proviso that at least one of the radicals R 1 and R 2 is not hydrogen.
Die erhältlichen urethangruppenhaltigen (Meth)acrylsäureester (U) können vorteilhaft als Comonomere in Poly(meth)acrylaten oder als Reaktivverdünner in strahlungshärtbaren und/oder Dual-Cure-härtbaren Poly(meth)acrylaten eingesetzt werden. Derartige Poly(meth)acrylate sind als Bindemittel in strahlungs- oder Dual-Cure-härtbaren Be- schichtungsmitteln geeignet. So erhältliche Beschichtungen weisen sehr hohe Kratzfestigkeiten, Härten, Chemikalienbeständigkeiten, Elastizität und Haftung, sowohl auf hydrophilen als auch auf hydrophoben Substraten auf.The available urethane group-containing (meth) acrylic esters (U) can advantageously be used as comonomers in poly (meth) acrylates or as reactive diluents in radiation-curable and / or dual-cure poly (meth) acrylates. Such poly (meth) acrylates are suitable as binders in radiation or dual-cure coating agents. Thus available coatings have very high scratch resistance, hardness, chemical resistance, elasticity and adhesion to both hydrophilic and hydrophobic substrates.
Eine weitere Verwendung der nach dem erfindungsgemäßen Verfahren hergestellten urethangruppenhaltigen (Meth)acrylsäureester (U) ist als Zusatz in Lackformulierungen möglich. Dabei können die urethangruppenhaltigen (Meth)acrylsäureester (U) sowohl in Basislacken als auch in Decklacken eingesetzt werden. Aufgrund ihrer besonderen Eigenschaften, wie der Erhöhung der Kratzfestigkeit und Elastizität, sowie der Erniedrigung der Viskosität, insbesondere bei verzweigten Polyacrylaten, einer strahlengehärteten Klarlackbeschichtung, ist ihr Einsatz in Deckbeschichtungen bevorzugt.A further use of the urethane group-containing (meth) acrylic esters (U) prepared by the process according to the invention is possible as an additive in coating formulations. The urethane group-containing (meth) acrylic esters (U) can be used both in basecoats and in topcoats. Because of their particular properties, such as increasing the scratch resistance and elasticity, as well as the lowering of the viscosity, especially in branched polyacrylates, a radiation-cured clearcoat, their use in topcoats is preferred.
Für eine solche Verwendung kann der urethangruppenhaltige (Meth)acrylsäureester (U) geeigneterweise mit einem Lösungsmittelzusatz abgemischt werden, um den festen Aggregatzustand zu verhindern und den urethangruppenhaltigen (Meth)acrylsäureester (U) in der flüssigen Phase zu halten. Dazu eignen sich damit mischbare niedere Kohlenwasserstoffe wie Methanol, Ethanol, Propanol, Isopropanol, Butanol, Hexanol und beliebige Mischungen davon. Üblicherweise werden 0 bis 40For such use, the urethane group-containing (meth) acrylic ester (U) may be suitably blended with a solvent additive to prevent the solid state and to keep the urethane group-containing (meth) acrylic acid ester (U) in the liquid phase. Miscible lower hydrocarbons such as methanol, ethanol, propanol, isopropanol, butanol, hexanol and any mixtures thereof are suitable for this purpose. Usually 0 to 40
Gew.-%, bevorzugt 5 bis 30 Gew.-% und besonders bevorzugt 10 bis 20 Gew.-% eines geeigneten Lösungsmittels, jeweils bezogen auf das Gesamtgewicht von Lösungsmittel und urethangruppenhaltigem (Meth)acrylsäureester (U), eingesetzt.Wt .-%, preferably 5 to 30 wt .-% and particularly preferably 10 to 20 wt .-% of a suitable solvent, in each case based on the total weight of solvent and urethane group-containing (meth) acrylic acid ester (U) used.
Die folgenden Beispiele sollen die Eigenschaften der Erfindung erläutern, ohne sie aber einzuschränken.The following examples are intended to illustrate the characteristics of the invention without, however, limiting it.
Falls nicht anders angegeben, bedeuten Prozent immer Gewichtsprozent und Teile immer Gewichtsteile.Unless otherwise indicated, percent are always weight percent and parts always parts by weight.
BeispieleExamples
Beispiel 1example 1
Herstellung von Hydroxypropylcarbamatacrylat
Preparation of hydroxypropyl carbamate acrylate
In einer Destillationsapparatur wurden zunächst 1000 g Hydroxypropylcarabamat (Isomerengemisch) mit 600 ml_ Methanol versetzt, und das Methanol anschließend unter Atmosphärendruck bei 50 0C abdestilliert. Es wurden erneut 600 g Methanol zugege- ben und abdestilliert. Anschließend wurde das Vakuum auf 3 mbar eingestellt und das restliche Lösungsmittel 30 Minuten lang bei 60 0C destillativ abgetrennt.In a distillation apparatus 1000 g Hydroxypropylcarabamat (mixture of isomers) were first mixed with 600 ml of methanol, and the methanol was then distilled off under atmospheric pressure at 50 0 C. Another 600 g of methanol were added and distilled off. The vacuum was then adjusted to 3 mbar and the residual solvent removed by distillation at 60 0 C for 30 minutes.
In einem Vorlagegefäß mit angeschlossener Doppelmantelglassäule, Pumpe und anschließendem 5L Vorratsgefäß wurde die Umesterung von Ethylacrylat mit Hydro- xypropylcarbamat durchgeführt. Die Doppelmantelglassäule (Länge 40 cm, Durchmesser 1 ,35 cm)war mit 14 mL Lipase (Novozym® 435) beschickt. Dann wurden 2002,4 g (20,0 mol) Ethylacrylat und 248,9 g (2,0 mol) des zuvor gereinigten Hydroxypropylcar- bamats in dem Vorlagengefäß miteinander vermischt. Zur Stabilisierung wurden 400,5 mg (200 ppm, bezogen auf Ethylacrylat) Hydrochinonmonomethylether zugege- ben. Die Temperatur wurde auf 40 0C eingestellt. Anschließend wurde mit Hilfe der Pumpe mit einer Geschwindigkeit von 1 1 mL pro Stunde die vorgelegte Reaktionsmischung über die mit Enzym beschickte Doppelmantelglassäule gepumpt und im Vorratsgefäß gesammelt.The transesterification of ethyl acrylate with hydroxypropyl carbamate was carried out in a receiving vessel with attached double-walled glass column, pump and subsequent 5 liter storage vessel. The double-walled glass column (length 40 cm, diameter 1, 35 cm) was charged with 14 mL of lipase (Novozym ® 435). Then, 2002.4 g (20.0 mol) of ethyl acrylate and 248.9 g (2.0 mol) of the previously purified hydroxypropyl carbamate were mixed together in the master vessel. For stabilization, 400.5 mg (200 ppm, based on ethyl acrylate) of hydroquinone monomethyl ether were added. The temperature was adjusted to 40 ° C. Subsequently, with the aid of the pump, the initially charged reaction mixture was pumped through the enzyme-loaded double-walled glass column at a rate of 1 1 ml per hour and collected in the storage vessel.
Nach 3 h 38 min betrug der Austrag im Vorratsgefäß 21 ,5 g. Der Umsatz betrugAfter 3 h 38 min, the discharge in the storage vessel was 21, 5 g. The turnover was
73,6 %. Anschließend wurde das erhaltene Rohprodukt mittels GC analysiert, es enthielt 53,9 % Hydroxypropylcarbamatacrylat.73.6%. Subsequently, the obtained crude product was analyzed by GC, containing 53.9% of hydroxypropyl carbamate acrylate.
Beispiel 2 Herstellung von Hydroxypropylcarbamatacrylat - LangzeitversuchExample 2 Preparation of Hydroxypropyl Carbamate Acrylate - Long Term Trial
Beispiel 1 wurde wiederholt. Die Pumpe wurde jedoch mit einer Geschwindigkeit von 15 mL/h betrieben. Die Reaktionszeit betrug insgesamt ca. 310 h, wobei nach verschiedenen Zeitabständen der Austrag im Vorratsgefäß, der Umsatz sowie die Reinheit mittels GC-Analyse bestimmt wurden. Die Ergebnisse sind in Tabelle 1 zusammenge- fasst.
Tabelle 1Example 1 was repeated. However, the pump was operated at a rate of 15 mL / h. The reaction time was a total of about 310 h, after different time intervals of the output in the storage vessel, the conversion and the purity were determined by GC analysis. The results are summarized in Table 1. Table 1
Man erkennt, dass das Leistungsoptimum des enzymatischen Festbettkatalysators bei ca. 1 Tag liegt, sowohl in Bezug auf den Umsatz als auch die Reinheit des Rohproduk- tes.It can be seen that the optimum performance of the enzymatic fixed-bed catalyst is about 1 day, both in terms of the conversion and the purity of the crude product.
Beispiel 3Example 3
Herstellung von Hydroxypropylcarbamatacrylat - Langzeitversuch mit 2. EnzymsäulePreparation of hydroxypropyl carbamate acrylate - long-term experiment with 2nd enzyme column
Von dem Austrag aus Beispiel 2 mit einer Reinheit von 52,9 % wurden 250 g (enthaltend 0,9 mol Hydroxypropylcarbamat) entnommen und mit 2010 g (20,08 mol) Ethylac- rylat versetzt. Bei einer Temperatur von 40 0C wurde diese Mischung über eine zweite, mit 12mL Lipase (Novozym® 435) beschickte Doppelmantelglassäule (Länge 40 cm, Durchmesser 1 ,35 cm) mit Hilfe einer Pumpe bei einer Geschwindigkeit von 15 mL/h geführt. Die Reaktionszeit betrug insgesamt ca. 160 h, wobei nach verschiedenen Zeitabständen der Austrag im Vorratsgefäß, der Umsatz sowie die Reinheit mittels GC- Analyse bestimmt wurden. Die Ergebnisse sind in Tabelle 2 zusammengefasst.From the effluent of Example 2 with a purity of 52.9%, 250 g (containing 0.9 mol of hydroxypropyl carbamate) were removed and admixed with 2010 g (20.08 mol) of ethyl acrylate. At a temperature of 40 0 C the mixture via a second, with 12 mL of lipase (Novozym ® 435) was charged jacketed glass column (length 35 cm 40 cm, diameter 1) guided by means of a pump at a rate of 15 mL / h. The reaction time was a total of about 160 h, wherein after various time intervals, the discharge in the storage vessel, the conversion and the purity were determined by GC analysis. The results are summarized in Table 2.
Tabelle 2Table 2
Es wird deutlich, dass ein zweiter enzymatischer Festbettkatalysator zu deutlich höheren Reinheiten des Rohproduktes führt. Das Leistungsoptimum liegt ebenfalls bei ca. 1 Tag, sowohl in Bezug auf den Umsatz als auch die Reinheit des Rohproduktes. It becomes clear that a second enzymatic fixed-bed catalyst leads to significantly higher purities of the crude product. The optimum performance is also about 1 day, both in terms of sales and the purity of the crude product.
Der gesamte Austrag nach Beendigung der Reaktion wurde in einem 2,5L Miniplantge- fäß gesammelt. Das Rohprodukt enthielt laut GC-Analyse 70,2 % Hydroxypropylcar- bamatacrylat. Das Rohrprodukt wurde anschließend mit 491 g vollentionisiertem Wasser gewaschen. Man erhielt 503,4 g wässrige Phase und eine organische Phase, die laut GC-Analyse 87,7 % Hydroxypropylcarbamatacrylat enthielt.The entire effluent after completion of the reaction was collected in a 2.5 L miniature flask. The crude product contained 70.2% hydroxypropylcarbamate acrylate according to GC analysis. The tube product was then washed with 491 g of deionized water. This gave 503.4 g of aqueous phase and an organic phase containing 87.7% hydroxypropyl carbamate according to GC analysis.
Diese organische Phase wurde nochmals mit 491 g vollentionisiertem Wasser gewaschen. Man erhielt 546,9 g wässrige Phase und eine organische Phase, die 93,7 % Hydroxypropylcarbamatacrylat (GC-Analyse) enthielt.This organic phase was washed again with 491 g of deionized water. This gave 546.9 g of aqueous phase and an organic phase containing 93.7% hydroxypropyl carbamate (GC) analysis.
Diese organische Phase wurde anschließend eingeengt. Es wurden 148,9 g Austrag erhalten, das Produkt wies eine Reinheit von 93,8 % auf (GC-Analyse)This organic phase was then concentrated. 148.9 g of product were obtained, the product had a purity of 93.8% (GC analysis)
Beispiel 4Example 4
Herstellung von HydroxypropylcarbamatacrylatPreparation of hydroxypropyl carbamate acrylate
Beispiel 1 wurde wiederholt. Die Reaktionstemperatur wurde jedoch auf 60 0C eingestellt. Die Pumpe wurde mit einer Geschwindigkeit von 15 mL/h betrieben.Example 1 was repeated. The reaction temperature, however, was set to 60 0 C. The pump was operated at a rate of 15 mL / h.
Nach 16 h 57 min betrug der Austrag im Vorratsgefäß 241 ,1 g. Der Umsatz betrug 71 ,0 %. Anschließend wurde das erhaltene Rohprodukt mittels GC analysiert, es enthielt 68,2 % Hydroxypropylcarbamatacrylat.After 16 h 57 min, the discharge in the storage vessel 241, 1 g. The conversion amounted to 71, 0%. Subsequently, the obtained crude product was analyzed by GC, containing 68.2% of hydroxypropyl carbamate acrylate.
Nach insgesamt 23 h 19 min wurde die Reaktion beendet. Der Austrag im Vorratsgefäß betrug 328,4 g Rohprodukt, dieses enthielt laut GC-Analyse 67,5 % Hydroxypro- pylcarbamatacrylat.
After a total of 23 h 19 min, the reaction was stopped. The discharge in the storage vessel was 328.4 g of crude product, this contained according to GC analysis 67.5% Hydroxyprop- pylcarbamatacrylat.
Claims
1. Verfahren zur Herstellung urethangruppenhaltiger (Meth)acrylsäureester (U) durch Umsetzung eines urethangruppenhaltigen Alkohols (A) mit einem (Meth)acrylsäureester eines gesättigten Alkohols (G) in Gegenwart mindestens eines Polymerisationsinhibitors (P) mit einem Enzym (E) als Katalysator in einem Reaktor, dadurch gekennzeichnet, dass der (Meth)acrylsäureester eines gesättigten Alkohols (G) und der urethangruppenhaltigen Alkohol (A) kontinuierlich ü- ber mindestens einen Festbettreaktor gefüllt mit einem immobilisierten Enzym (E) als Katalysator geleitet werden.1. A process for the preparation of urethane group-containing (meth) acrylic ester (U) by reacting a urethane group-containing alcohol (A) with a (meth) acrylic ester of a saturated alcohol (G) in the presence of at least one polymerization inhibitor (P) with an enzyme (E) as a catalyst in a reactor, characterized in that the (meth) acrylic acid ester of a saturated alcohol (G) and the urethane group-containing alcohol (A) continuously ü over at least one fixed bed reactor filled with an immobilized enzyme (E) are passed as a catalyst.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass der urethangruppen- haltige Alkohol (A) erhältlich ist durch folgende Reaktion2. The method according to claim 1, characterized in that the urethane group-containing alcohol (A) is obtainable by the following reaction
worinwherein
R1, R2 unabhängig voneinander Wasserstoff, Ci-Cis-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C2-Ci8-Alkyl, C2-Ci8-Alkenyl, C6-Ci2-Aryl, C5-Ci2-Cycloalkyl oder einen fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus, wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiert sein können, oder eine Gruppe der Formel -[X,]k-H,R 1 , R 2 independently of one another are hydrogen, C 1 -C 6 -alkyl, C 2 -C -alkyl which is optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 -C -alkenyl , C 6 -C 2 aryl, C 5 -C 2 cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-containing heterocycle, where the radicals in each case by aryl, alkyl, aryloxy, alkyloxy, heteroatoms mentioned and / or heterocycles, or a group of the formula - [X,] kH,
Xi für jedes i = 1 bis k unabhängig voneinander ausgewählt sein kann aus der Gruppe -CH2-CH2-O-, -CH2-CH2-N(H)-, -CH2-CH2-CH2-N(H)-, -CH2-CH(NH2)-, -CH2-CH(NHCHO)-, -CH2-CH(CHs)-O-, -CH(CHs)-CH2-O-, -CH2-C(CH3)2-O-, -C(CHs)2-CH2-O-, -CH2-CH2-CH2-O-, -CH2-CH2-CH2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O- und -CHPh-CH2-O-, worin Ph für Phenyl und Vin für Vinyl steht,Xi for each i = 1 to k can be independently selected from the group -CH 2 -CH 2 -O-, -CH 2 -CH 2 -N (H) -, -CH 2 -CH 2 -CH 2 -N (H) -, -CH 2 -CH (NH 2 ) -, -CH 2 -CH (NHCHO) -, -CH 2 -CH (CHs) -O-, -CH (CHs) -CH 2 -O-, -CH 2 -C (CH 3 ) 2 -O-, -C (CH 2 ) 2 -CH 2 -O-, -CH 2 -CH 2 -CH 2 -O-, -CH 2 -CH 2 -CH 2 - CH 2 -O-, -CH 2 -CHVin-O-, -CHVin-CH 2 -O-, -CH 2 -CHPh-O- and -CHPh-CH 2 -O-, where Ph is phenyl and Vin is vinyl stands,
k für eine Zahl von 1 bis 50 undk for a number from 1 to 50 and
Y C2-C2O-AI kylen oder durch ein- oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte I- minogruppen und/oder durch eine oder mehrere -(CO)-, -0(CO)O-, -
(NH)(CO)O-, -0(CO)(NH)-, -0(CO)- oder -(CO)O-Gruppen unterbrochenes C2-C2o-Alkylen, wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiert sein können,YC 2 -C 2 O-Al kylene or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted I- minogruppen and / or by one or more - (CO) -, -0 (CO ) O-, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O- groups interrupted C2-C2o-alkylene, wherein the radicals mentioned in each case by aryl, alkyl, Aryloxy, alkyloxy, heteroatoms and / or heterocycles may be substituted,
bedeuten.mean.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass R1 und R2 unabhängig voneinander Wasserstoff, Ci-Ci2-Alkyl, Cs-Cβ-Cycloalkyl oder eine Gruppe der Formel -[X,]k-H sind.3. The method according to claim 2, characterized in that R 1 and R 2 are independently hydrogen, Ci-Ci2-alkyl, Cs-Cβ-cycloalkyl or a group of the formula - [X,] kH.
4. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der (Meth)acrylsäureester eines gesättigten Alkohols ausgewählt ist aus der Gruppe (Meth)acrylsäuremethyl-, -ethyl-, -n-butyl- und 2-ethylhexylester.4. The method according to any one of the preceding claims, characterized in that the (meth) acrylic acid ester of a saturated alcohol is selected from the group (meth) acrylic acid methyl, ethyl, n-butyl and 2-ethylhexylester.
5. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass es sich bei dem Enzym (E) um eine Lipase handelt.5. The method according to any one of the preceding claims, characterized in that it is the enzyme (E) is a lipase.
6. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der (Meth)acrylsäureester des gesättigten Alkohols (G) mit dem urethan- gruppenhaltigen Alkohol (A) zuvor miteinander vermischt werden, und diese Reaktionsmischung anschließend über das mindestens eine immobolisierte Enzym (E) geleitet wird.6. The method according to any one of the preceding claims, characterized in that the (meth) acrylic acid ester of the saturated alcohol (G) with the urethane group-containing alcohol (A) are previously mixed together, and this reaction mixture then on the at least one immobilized enzyme (E ).
7. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das molare Verhältnis von (Meth)acrylsäureester eines gesättigten Alkohols (G) zu urethangruppenhaltigen Alkohol (A) im Bereich von 50:1 bis 1 :1 liegt.7. The method according to any one of the preceding claims, characterized in that the molar ratio of (meth) acrylic acid ester of a saturated alcohol (G) to urethane group-containing alcohol (A) in the range of 50: 1 to 1: 1.
8. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Rohprodukt destillativ gereinigt wird, wobei das Azeotrop aus freiwerdendem gesättigten Alkohol und überschüssigem korrespondierendem (Meth)acrylsäureester (G) und gegebenenfalls verwendetem Schleppmittel abgetrennt wird.8. The method according to any one of the preceding claims, characterized in that the crude product is purified by distillation, wherein the azeotrope is separated from liberated saturated alcohol and excess corresponding corresponding (meth) acrylic acid ester (G) and optionally used entraining agent.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass der destillativ aufgereinigte urethangruppenhaltige (Meth)acrylsäureester (U) über einen weiteren, mit immobilisiertem Enzym (E) beschickten Festbettreaktor geleitet wird.9. The method according to claim 8, characterized in that the distillatively purified urethane group-containing (meth) acrylic acid ester (U) via another, with immobilized enzyme (E) fed fixed bed reactor is passed.
10. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der urethangruppenhaltige (Meth)acrylsäureester (U) einem Extraktionsvorgang mit Wasser unterzogen wird.
10. The method according to any one of the preceding claims, characterized in that the urethane group-containing (meth) acrylic acid ester (U) is subjected to an extraction process with water.
1. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass urethangruppenhaltige Alkohol (A) aufgereinigt eingesetzt wird, in dem der urethangruppenhaltige Alkohol (A) zuvor durch eine kontinuierliche Reindestillation von leicht- und schwersiedenden Nebenkomponenten abgetrennt wird.
1. The method according to any one of the preceding claims, characterized in that urethane group-containing alcohol (A) is used purified, in which the urethane group-containing alcohol (A) is previously separated by a continuous purifying distillation of low-boiling and high-boiling secondary components.
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US17729209P | 2009-05-12 | 2009-05-12 | |
DE102009003036A DE102009003036A1 (en) | 2009-05-12 | 2009-05-12 | Process for the continuous production of urethane group-containing (meth) acrylic acid esters |
PCT/EP2010/056138 WO2010130616A1 (en) | 2009-05-12 | 2010-05-06 | Method for the continuous production of (meth)acrylic acid esters containing urethane groups |
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EP2430071A1 true EP2430071A1 (en) | 2012-03-21 |
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EP10717647A Withdrawn EP2430071A1 (en) | 2009-05-12 | 2010-05-06 | Method for the continuous production of (meth)acrylic acid esters containing urethane groups |
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US (1) | US8263370B2 (en) |
EP (1) | EP2430071A1 (en) |
JP (1) | JP2012526525A (en) |
KR (1) | KR20120046109A (en) |
CN (1) | CN102421823B (en) |
DE (1) | DE102009003036A1 (en) |
WO (1) | WO2010130616A1 (en) |
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EP2438179B1 (en) | 2009-06-04 | 2016-12-21 | Basf Se | A process for the enzymatic reduction of enoates |
WO2011092345A1 (en) | 2010-02-01 | 2011-08-04 | Basf Se | Process for the reduction of cinnamaldehyde derivative employing enoate reductases |
DE202012001123U1 (en) | 2012-02-06 | 2012-04-26 | Basf Se | Adhesive article prepared with a urethane group-containing (meth) acrylic acid ester-based copolymer |
US20130273619A1 (en) | 2012-04-16 | 2013-10-17 | Basf Se | Process for the Preparation of (3E, 7E)-Homofarnesol |
RU2015155833A (en) * | 2013-05-31 | 2017-07-06 | ДСМ АйПи АССЕТС Б.В. | IMMOBILIZED PROLINSPECIFIC ENDOPROTEASE |
CN104356288A (en) * | 2014-11-25 | 2015-02-18 | 烟台市牟平区留德润滑油销售有限公司 | Production method of pour point depressing and turbidity reducing agent for waste oil recovered lubricant base oil |
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---|---|---|---|---|
GB8323897D0 (en) | 1983-09-06 | 1983-10-05 | Exxon Research Engineering Co | Copolymerisation of unsaturated esters |
US4820830A (en) | 1987-03-02 | 1989-04-11 | King Industries, Inc. | Certain hydroxyalkyl carbamates, polymers and uses thereof |
US5240835A (en) | 1989-10-10 | 1993-08-31 | Genencor International, Inc. | Methods for enzymatically preparing polymerizable monomers |
CN1072686C (en) * | 1997-07-10 | 2001-10-10 | 中国科学院长春应用化学研究所 | Synthetic process of photofixed polyester propenoic methyl carbamate |
JP2001040039A (en) | 1999-07-30 | 2001-02-13 | Dainippon Ink & Chem Inc | Activated energy rays-hardenable composition |
WO2004005088A1 (en) | 2002-07-05 | 2004-01-15 | Paul Marriott | Intrusion detector |
DE10257094A1 (en) * | 2002-12-05 | 2004-06-24 | Basf Ag | Enzymatic production of (meth) acrylic acid esters containing urethane groups |
DE10305313A1 (en) * | 2003-02-10 | 2004-08-26 | Basf Coatings Ag | Ester conjugated unsaturated acids (conjugate esters), process for their preparation and their use |
JP2007538021A (en) * | 2004-05-17 | 2007-12-27 | サイテック サーフェース スペシャリティーズ、エス.エイ. | Method for producing urethane (meth) acrylate and novel urethane (meth) acrylate |
DE102005016225A1 (en) | 2005-04-07 | 2006-07-06 | Basf Ag | Production of a binary mixture of structural isomer beta-hydroxy-alkyl-carbamates, for paints and adhesives, where the 1,2-alkylene carbonate in a formulation is converted with ammonia or a primary/secondary amine |
DE102005016252B3 (en) | 2005-04-08 | 2007-02-15 | Metzeler Automotive Profile Systems Gmbh | Device for detecting an obstacle in the opening region of a power-operated closing element, in particular a window pane of a motor vehicle |
KR100724797B1 (en) * | 2005-10-10 | 2007-06-04 | 에스에스씨피 주식회사 | Low viscosity multi-functional urethaneacrylate oligomer-containing high solid uv curable coating composition |
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JP2012526525A (en) | 2012-11-01 |
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KR20120046109A (en) | 2012-05-09 |
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