CN103958567B - 烷氧基化聚亚烷基多胺 - Google Patents
烷氧基化聚亚烷基多胺 Download PDFInfo
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- CN103958567B CN103958567B CN201280057887.7A CN201280057887A CN103958567B CN 103958567 B CN103958567 B CN 103958567B CN 201280057887 A CN201280057887 A CN 201280057887A CN 103958567 B CN103958567 B CN 103958567B
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- polyalkylene polyamine
- alkoxylate
- catalyst
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- 229920000768 polyamine Polymers 0.000 title claims abstract description 88
- 229920001281 polyalkylene Polymers 0.000 title claims abstract description 65
- -1 aliphatic amino alcohols Chemical class 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005576 amination reaction Methods 0.000 claims abstract description 13
- 239000002815 homogeneous catalyst Substances 0.000 claims abstract description 13
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007172 homogeneous catalysis Methods 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 230000007797 corrosion Effects 0.000 claims abstract description 4
- 238000005260 corrosion Methods 0.000 claims abstract description 4
- 239000003599 detergent Substances 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 239000003112 inhibitor Substances 0.000 claims abstract description 4
- 239000004753 textile Substances 0.000 claims abstract description 3
- 239000003171 wood protecting agent Substances 0.000 claims abstract description 3
- 229920005862 polyol Polymers 0.000 claims abstract 2
- 150000003077 polyols Chemical class 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 29
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000003446 ligand Substances 0.000 claims description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 150000003623 transition metal compounds Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000011877 solvent mixture Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000008030 elimination Effects 0.000 abstract description 2
- 238000003379 elimination reaction Methods 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 41
- 239000000047 product Substances 0.000 description 31
- 239000002585 base Substances 0.000 description 24
- 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 22
- 150000001412 amines Chemical class 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 16
- 150000005846 sugar alcohols Polymers 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 150000001721 carbon Chemical group 0.000 description 12
- 150000003141 primary amines Chemical class 0.000 description 10
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000001118 alkylidene group Chemical group 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002608 ionic liquid Substances 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 150000003335 secondary amines Chemical class 0.000 description 8
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 125000002015 acyclic group Chemical group 0.000 description 7
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000003512 tertiary amines Chemical class 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 150000001541 aziridines Chemical class 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 5
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 3
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 3
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- YSRSBDQINUMTIF-UHFFFAOYSA-N decane-1,2-diol Chemical compound CCCCCCCCC(O)CO YSRSBDQINUMTIF-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 3
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 3
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 2
- YXEFFHITYOBLCN-UHFFFAOYSA-N 1-adamantyl(butyl)phosphane Chemical class C1C(C2)CC3CC2CC1(PCCCC)C3 YXEFFHITYOBLCN-UHFFFAOYSA-N 0.000 description 2
- GEZGAZKEOUKLBR-UHFFFAOYSA-N 1-phenylpyrrole Chemical compound C1=CC=CN1C1=CC=CC=C1 GEZGAZKEOUKLBR-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- ZITKDVFRMRXIJQ-UHFFFAOYSA-N dodecane-1,2-diol Chemical compound CCCCCCCCCCC(O)CO ZITKDVFRMRXIJQ-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229940031098 ethanolamine Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- GJBXIPOYHVMPQJ-UHFFFAOYSA-N hexadecane-1,16-diol Chemical compound OCCCCCCCCCCCCCCCCO GJBXIPOYHVMPQJ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000005451 methyl sulfates Chemical class 0.000 description 2
- 229950000081 metilsulfate Drugs 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N n-pentylamine Natural products CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- WHAFDJWJDDPMDO-UHFFFAOYSA-N trimethyl(phenyl)phosphanium Chemical compound C[P+](C)(C)C1=CC=CC=C1 WHAFDJWJDDPMDO-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 2
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- CQTBQILMJBCTRS-UHFFFAOYSA-N tetradecane-1,1-diol Chemical class CCCCCCCCCCCCCC(O)O CQTBQILMJBCTRS-UHFFFAOYSA-N 0.000 description 1
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Abstract
制备烷氧基化聚亚烷基多胺的方法,包括下列步骤:(a)均相催化醇胺化,其中在均相催化剂存在下在消除水下使脂族氨基醇相互反应或者使脂族二胺或多胺与脂族二醇或多元醇反应,得到聚亚烷基多胺,(b)使这些聚亚烷基多胺与氧化烯反应而得到烷氧基化聚亚烷基多胺。可以通过该类方法得到的具体烷氧基化聚亚烷基多胺以及烷氧基化聚亚烷基多胺及其制备方法。烷氧基化聚亚烷基多胺作为洗涤添加剂、分散剂、织物助剂、木材保护剂、腐蚀抑制剂的用途。
Description
本发明涉及一种通过使氧化烯与通过链烷醇胺的均相催化醇胺化或二-或多胺与二醇或多元醇的均相催化醇胺化制备的聚亚烷基多胺反应而制备烷氧基化聚亚烷基多胺的方法。此外,本发明还涉及可以通过这些方法得到的烷氧基化聚亚烷基多胺以及烷氧基化聚亚烷基多胺的用途。本发明进一步提供了特定烷氧基化聚亚烷基多胺及其制备。
本发明的其他实施方案可以在权利要求书、说明书和实施例中找到。不用说上面已经描述且下文仍待解释的本发明主题的特征不仅可以以在每种情况下具体说明的组合使用,而且在不背离本发明范围下以其他组合使用。分别优选或非常优选其中所有特征具有优选或非常优选含义的本发明实施方案。
聚乙烯亚胺类是具有大量不同用途的有价值产物。例如,将聚乙烯亚胺类a)用作用于层压薄膜的印刷油墨用促粘剂;b)用作生产多层复合薄膜的助剂(粘附),其中不仅将不同的聚合物层相容化,而且使金属薄膜相容化;c)用作粘合剂用促粘剂,例如与聚乙烯醇、聚丁酸乙烯酯和聚乙酸乙烯酯以及苯乙烯共聚物一起,或用作标签粘合剂用内聚促进剂;d)此外可以将低分子量聚乙烯亚胺类在环氧树脂和聚氨酯粘合剂中用作交联剂/硬化剂;e)在涂料应用中用作改善在基材如玻璃、木材、塑料和金属上的粘附的底漆;f)用于在标准乳胶漆中改善湿粘以及还用于改善例如用于路面标记的油漆的瞬时耐雨性;g)用作对重金属如Hg、Pb、Cu、Ni具有高结合能力的配位剂以及水处理/水加工中的絮凝剂;h)在木材防腐中用作活性金属盐配制剂的渗透助剂;i)用作铁和非铁金属的腐蚀抑制剂;j)用于蛋白质和酶的固定化。对于这些应用,还可以使用不是衍生于该乙烯亚胺的聚亚烷基多胺。
聚乙烯亚胺类目前通过乙烯亚胺的均聚得到。乙烯亚胺是可以以不同方式合成的高度反应性、腐蚀性和毒性中间体(氮丙啶类,Ulrich Steuerle,Robert Feuerhake;Ullmann′s Encyclopedia of Industrial Chemistry,2006,Wiley-VCH,Weinheim)。
在β-氯乙基胺方法中,乙烯亚胺通过使β-氯乙基胺与NaOH反应而得到。该方法可能导致β-氯乙基胺通过HCl消除而不希望地聚合,这必须小心避免。此外,使用2当量NaOH和形成联产物NaCl是不利的。
在Dow方法中,该乙烯亚胺可以通过使1,2-二氯乙烷与3当量氨反应而得到。使用大量氨,不利的是形成联产物氯化铵、反应混合物的腐蚀性以及还有产物中的杂质。
在Wencker方法中,在第一步中使2-氨基乙醇与硫酸反应得到2-氨基乙基硫酸氢酯。然后在第二步中通过加入2当量NaOH而由其得到该乙烯胺。这里也不利的是使用硫酸和NaOH以及还有形成联产物硫酸钠。
在2-氨基乙醇的催化脱氢过程中,该乙烯亚胺通过2-氨基乙醇在气相中在250-450℃下催化脱氢而得到。该方法的缺点是配合物产物通过蒸馏后处理、高能量要求以及还有短催化剂寿命。
除了这些制备乙烯亚胺的方法的所述缺点外,由该起始化合物开始合成聚乙烯亚胺是有问题的,因为必须处理该高度反应性、毒性和腐蚀性乙烯亚胺。同样必须确保没有乙烯亚胺残留在所得产物和/或废水料流中。
对于制备不是衍生于氮丙啶的具有亚烷基>C2(x>2)的聚亚烷基多胺-[(CH2)xN]-,没有类似于该氮丙啶途径的方法,因此迄今为止对其制备尚无成本有效的方法。
由文献已知醇的均相催化胺化用于由醇和胺开始合成伯、仲和叔胺,其中在所有所述实施方案中得到单体型产物。
US3,708,539描述了使用钌-磷烷配合物合成伯、仲和叔胺。
Y.Watanabe,Y.Tsuji,Y.Ohsugi Tetrahedron Lett.1981,22,2667-2670报道了通过使用[Ru(PPh3)3Cl2]作为催化剂将醇用苯胺胺化而制备芳基胺。
EP0034480A2公开了使用铱、铑、钌、锇、铂、钯或铼催化剂通过伯或仲胺与伯或仲醇的反应制备N-烷基-或N,N-二烷基胺。
EP0239934A1描述了由二醇如乙二醇和1,3-丙二醇与仲胺开始使用钌和铱磷烷配合物合成单-和二胺化产物。
K.I.Fujita,R.Yamaguchi Synlett,2005,4,560-571描述了通过醇与伯胺反应合成仲胺以及还有通过伯胺与二醇通过使用铱催化剂的闭环反应而合成环状胺。
在A.Tillack,D.Hollmann,K.Mevius,D.Michalik,S.M.BellerEur.J.Org.Chem.2008,4745-4750;A.Tillack,D.Hollmann,D.Michalik,M.Beller Tetrahedron Lett.2006,47,8881-8885;D.Hollmann,S.A.Tillack,M.Beller Angew.Chem.Int.Ed.2007,46,8291-8294以及M.Haniti,S.A.Hamid,C.L.Allen,G.W.Lamb,A.C.Maxwell,H.C.Maytum,A.J.A.Watson,J.M.J.Williams J.Am.Chem.Soc,2009,131,1766-1774中描述了由醇和伯或仲胺开始使用均相钌催化剂合成仲和叔胺。
通过使醇与氨使用均相钌催化剂反应而合成伯胺报道在C.Gunanathan,D.Milstein Angew.Chem.Int.Ed.2008,47,8661-8664中。
我们未公布的申请PCT/EP2011/058758描述了通过链烷醇胺的催化醇胺化或者二胺或多胺与二醇或多元醇的催化醇胺化制备聚亚烷基多胺的通用方法。
烷氧基化多胺如烷氧基化聚乙烯亚胺广泛用作例如洗涤添加剂、分散剂、织物助剂、木材保护剂、腐蚀抑制剂。烷氧基化聚乙烯亚胺的用途例如描述于专利说明书US4891260、US4647921、US4654043和US4645611中。
本发明的目的是要找到一种制备烷氧基化聚亚烷基多胺的方法,其中不使用氮丙啶,不形成不希望的联产物且得到具有所需链长的产物。
该目的由一种制备烷氧基化聚亚烷基多胺的方法实现,该方法包括如下步骤:(a)均相催化醇胺化,其中在均相催化剂存在下(i)使脂族氨基醇相互反应或(ii)使脂族二胺或多胺与脂族二醇或多元醇在消除水下反应,得到聚亚烷基多胺,以及(b)使这些聚亚烷基多胺与氧化烯反应而得到烷氧基化聚亚烷基多胺。
在本发明范围内,形式Ca-Cb的表述是指具有一定碳原子数的化学化合物或取代基。碳原子数可以选自a-b的整个范围,包括a和b,a至少为1且b总是大于a。化学化合物或取代基进一步由形式Ca-Cb-V的表述表示。V在这里表示化学化合物类别或取代基类别,例如烷基化合物或烷基取代基。
具体而言,对各取代基所述集合性术语具有下列含义:
C1-C50烷基:具有至多50个碳原子的直链或支化烃基,例如C1-C10烷基或C11-C20烷基,优选C1-C10烷基,例如C1-C3烷基,如甲基、乙基、丙基、异丙基,或C4-C6烷基,正丁基、仲丁基、叔丁基、1,1-二甲基乙基、戊基、2-甲基丁基、1,1-二甲基丙基、1,2-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、己基、2-甲基戊基、3-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基,或C7-C10烷基,如庚基、辛基、2-乙基己基、2,4,4-三甲基戊基、1,1,3,3-四甲基丁基、壬基或癸基及其异构体。
C3-C15环烷基:具有3-15个碳环成员的单环饱和烃基,优选C3-C8环烷基如环丙基、环丁基、环戊基、环己基、环庚基或环辛基,以及还有饱和或不饱和环状体系如降冰片基或降冰片烯基。
芳基:包含6-14个碳环成员的单核至三核芳族环体系,例如苯基、萘基或蒽基,优选单核至二核芳族环体系,特别优选单核芳族环体系。
在本发明范围内,符号“*”对所有化学化合物而言表示一个化学基团经由其键合于另一化学基团的价键。
适合本发明方法步骤(a)的脂族氨基醇包含至少一个伯或仲氨基和至少一个OH基团。实例是线性、支化或环状链烷醇胺,如单乙醇胺,二乙醇胺,氨基丙醇,例如3-氨基丙-1-醇或2-氨基丙-1-醇,氨基丁醇,例如4-氨基丁-1-醇、2-氨基丁-1-醇或3-氨基丁-1-醇,氨基戊醇,例如5-氨基戊-1-醇或1-氨基戊-2-醇,氨基二甲基戊醇,例如5-氨基-2,2-二甲基戊醇,氨基己醇,例如2-氨基己-1-醇或6-氨基己-1-醇,氨基庚醇,例如2-氨基庚-1-醇或7-氨基庚-1-醇,氨基辛醇,例如2-氨基辛-1-醇或8-氨基辛-1-醇,氨基壬醇,例如2-氨基壬-1-醇或9-氨基壬-1-醇,氨基癸醇,例如2-氨基癸-1-醇或10-氨基癸-1-醇,氨基十一烷醇,例如2-氨基十一烷-1-醇或11-氨基十一烷-1-醇,氨基十二烷醇,例如2-氨基十二烷-1-醇或12-氨基十二烷-1-醇,氨基十三烷醇,例如2-氨基十三烷-1-醇,1-(2-羟基乙基)哌嗪,2-(2-氨基乙氧基)乙醇,烷基链烷醇胺,例如丁基乙醇胺、丙基乙醇胺、乙基乙醇胺、甲基乙醇胺。特别优选单乙醇胺和单丙醇胺。
适合本发明方法步骤(a)的脂族二胺包含至少两个伯氨基或至少一个伯氨基和至少一个仲氨基或至少两个仲氨基,它们优选包含两个伯氨基。实例是线性、支化或环状脂族二胺。实例是乙二胺,1,3-丙二胺,1,2-丙二胺,丁二胺,例如1,4-丁二胺或1,2-丁二胺,二氨基戊烷,例如1,5-二氨基戊烷或1,2-二氨基戊烷、1,5-二氨基-2-甲基戊烷,二氨基己烷,例如1,6-二氨基己烷或1,2-二氨基己烷,二氨基庚烷,例如1,7-二氨基庚烷或1,2-二氨基庚烷,二氨基辛烷,例如1,8-二氨基辛烷或1,2-二氨基辛烷,二氨基壬烷,例如1,9-二氨基壬烷或1,2-二氨基壬烷,二氨基癸烷,例如1,10-二氨基癸烷或1,2-二氨基癸烷,二氨基十一烷,例如1,11-二氨基十一烷或1,2-二氨基十一烷,二氨基十二烷,例如1,12-二氨基十二烷或1,2-二氨基十二烷,3,3′-二甲基-4,4′-二氨基二环己基甲烷,4,4′-二氨基二环己基甲烷,异佛尔酮二胺,2,2-二甲基-1,3-丙二胺,4,7,10-三氧杂-1,13-十三烷二胺,4,9-二氧杂-1,12-十二烷二胺,聚醚胺,哌嗪,3-(环己基氨基)丙基胺,3-(甲基氨基)丙基胺,N,N-二(3-氨基丙基)甲基胺。
适合步骤(a)的脂族二醇是线性、支化或环状脂族二醇。脂族二醇的实例是乙二醇,1,2-丙二醇,1,3-丙二醇,2-甲基-1,3-丙二醇,丁二醇类,例如1,4-丁二醇或2,3-丁二醇或1,2-丁二醇,戊二醇类,例如新戊二醇或1,5-戊二醇或1,2-戊二醇,己二醇类,例如1,6-己二醇或1,2-己二醇,庚二醇类,例如1,7-庚二醇或1,2-庚二醇,辛二醇类,例如1,8-辛二醇或1,2-辛二醇,壬二醇类,例如1,9-壬二醇或1,2-壬二醇,癸二醇类,例如1,10-癸二醇或1,2-癸二醇,十一烷二醇类,例如1,11-十一烷二醇或1,2-十一烷二醇,十二烷二醇类,例如1,12-十二烷二醇,1,2-十二烷二醇,十三烷二醇类,例如1,13-十三烷二醇或1,2-十三烷二醇,十四烷二醇类,例如1,14-十四烷二醇或1,2-十四烷二醇,十五烷二醇类,例如1,15-十五烷二醇或1,2-十五烷二醇,十六烷二醇类,例如1,16-十六烷二醇或1,2-十六烷二醇,十七烷二醇类,例如1,17-十七烷二醇或1,2-十七烷二醇,十八烷二醇类,例如1,18-十八烷二醇或1,2-十八烷二醇,3,4-二甲基-2,5-己二醇,聚THF,1,4-二(2-羟基乙基)哌嗪,二乙醇胺类,例如丁基二乙醇胺或甲基二乙醇胺,二醇胺和三醇胺。
可以根据本发明得到的优选烷氧基化聚亚烷基多胺和/或可以在步骤(a)中得到的聚亚烷基多胺包含C2-C50亚烷基单元,特别优选C2-C20亚烷基单元。这些可以是线性或支化的,优选它们是线性的。实例是亚乙基,亚丙基,例如1,3-亚丙基,亚丁基,例如1,4-亚丁基,亚戊基,例如1,5-亚戊基或1,2-亚戊基,亚己基,例如1,6-亚己基,亚辛基,例如1,8-亚辛基或1,2-亚辛基,亚壬基,例如1,9-亚壬基或1,2-亚壬基,亚癸基,例如1,2-亚癸基或1,10-亚癸基,亚十一烷基,例如1,2-亚十一烷基,亚十二烷基,例如1,12-亚十二烷基或1,2-亚十二烷基,亚十三烷基,例如1,2-亚十三烷基,辛基,壬基,癸基,十一烷基,十二烷基,十三烷基,亚新戊基。亚环烷基单元也是可能的,例如1,3-或1,4-亚环己基。该烷氧基化聚亚烷基多胺特别优选具有C2亚烷基单元。
还可以在步骤(a)的相应反应中使用脂族氨基醇的混合物或链烷二醇的混合物或二氨基链烷烃的混合物。在步骤(a)中得到的聚亚烷基多胺可以包含不同长度的亚烷基单元。
在步骤(a)中也可以使具有不止一个OH基团或不止一个伯或仲氨基的多官能氨基醇相互反应。此时得到高度支化产物。多官能氨基醇的实例是二乙醇胺、N-(2-氨基乙基)乙醇胺、二异丙醇胺、二异壬醇胺、二异癸醇胺、二异十一烷醇胺、二异十二烷醇胺、二异十三烷醇胺。
在步骤(a)中也可以使多元醇或二醇和多元醇的混合物与二胺反应。多胺或二胺和多胺的混合物也可以与二醇反应。多元醇或二醇和多元醇的混合物也可以与多胺或二胺和多胺的混合物反应。此时得到高度支化产物。
多元醇实例是甘油、三羟甲基丙烷、山梨醇、三乙醇胺、三异丙醇胺。多胺的实例是二亚乙基三胺、三(氨基乙基)胺、三嗪、3-(2-氨基乙基氨基)丙基胺、二亚丙基三胺、N,N′-二(3-氨基丙基)乙二胺。
在步骤(a)中特别合适的化合物是其中原料脂族氨基醇、脂族二胺或多胺或脂族二醇或多元醇中的至少一种包含具有2-4个碳原子的烷基或亚烷基的那些。
特别适合在步骤(a)中的反应的化合物同样是其中原料脂族氨基醇、脂族二胺或多胺或脂族二醇或多元醇中的至少一种包含具有5个或更多个,优选7个或更多个,特别优选9个或更多个,尤其是12个或更多个碳原子的烷基或亚烷基的那些。
在步骤(a)中特别合适的化合物是其中原料脂族氨基醇、脂族二胺或多胺或脂族二醇或多元醇中的至少一种包含具有5-50个,优选5-20个,特别优选6-18个,非常特别优选7-16个,尤其优选8-14个,尤其是9-12个碳原子的烷基或亚烷基的那些。
对于在步骤(a)中的合成,优选至少选择(i)单乙醇胺、单丙醇胺或(ii)乙二醇与乙二胺。此外,优选至少选择(ii)乙二胺或1,2-丙二胺或1,3-丙二胺和1,2-癸二醇或1,2-十二烷二醇。
二醇、多元醇和二胺、多胺中的羟基和氨基在步骤(a)中优选以20:1-1:20,特别优选8:1-1:8,尤其是3:1-1:3的摩尔比使用。
聚亚烷基多胺也可以在步骤(a)中反应。在该反应过程中可以加入二胺或多胺或二醇或多元醇或氨基醇。
在步骤(a)中制备聚亚烷基多胺作为举例由方程1和2说明:
方程2
在本发明方法的优选实施方案中,在步骤(a)中在反应之后,优选在冷却之后,尤其在冷却至室温之后,优选在加入优选极性的溶剂,尤其是水之后,存在得到至少一个非极性相和至少一个极性相的相分离。这里该聚亚烷基多胺特别优选富集在该非极性相中,尤其是包含具有5个或更多个碳原子的烷基或亚烷基的那些聚亚烷基多胺。特别优选该均相催化剂富集在该极性相中。
均相催化剂应理解为指在反应过程中以均相溶解形式存在于反应介质中的催化剂。
该均相催化剂通常包含至少一种元素周期表副族元素(过渡金属)。在步骤(a)中的醇胺化可以在额外溶剂存在或不存在下进行。醇胺化可以在多相,优选一相或两相液体体系中在通常为20-250℃的温度下进行。在两相反应体系的情况下,上层相可以由包含大部分均相溶解的催化剂的非极性溶剂构成,而下层相包含极性原料、形成的多胺以及还有水。此外,下层相可以由水以及还有均相溶解的催化剂构成,而上层相可以由包含大部分形成的多胺和非极性原料的非极性溶剂构成。
在本发明的优选实施方案中,在步骤(a)中使(i)单乙醇胺或(ii)单丙醇胺或(iii)选自乙二胺、1,3-丙二胺或1,2-丙二胺的二胺与选自乙二醇、1,2-癸二醇或1,2-十二烷二醇的二醇在均相催化剂存在下在1-10MPa的氢气压力下且在除去反应过程中形成的水下反应。
该聚亚烷基多胺中的亚烷基单元数n通常为3-50000。
在步骤(a)中如此得到的聚亚烷基多胺可以带有NH2以及还有OH基团二者作为链端的端基。
其中优选
R相互独立地相同或不同且为H、C1-C50烷基,
l、m相互独立地相同或不同且为1-50,优选1-30,特别优选1-20的整数,n、k相互独立地相同或不同且为0-50,优选0-30,特别优选0-20的整数,i为3-50000的整数。
在步骤(a)中得到的聚亚烷基多胺的数均分子量Mn通常为200-2000000,优选400-750000,特别优选400-50000。摩尔质量分布Mw/Mn通常为1.2-20,优选1.5-7.5。阳离子电荷密度(在pH4-5下)通常为4-22mequ/g干物质,优选6-18mequ/g。
根据步骤(a)得到的聚亚烷基多胺可以以线性形式或以支化或多重支化形式存在并且也具有环形结构单元:
就此而言,结构单元(线性、支化或环状)的分布是无规的。如此得到的聚亚烷基多胺与由乙烯亚胺得到的聚乙烯亚胺的不同在于存在的OH端基以及还有任选的不同亚烷基。
在步骤(a)中的均相催化剂优选为包含一种或多种元素周期表副族的不同金属,优选至少一种选自元素周期表第8、9和10族的元素,特别优选钌或铱的过渡金属配合物催化剂。所述副族金属以配合物形式存在。使用许多不同的配体。
存在于过渡金属配合物中的合适配体例如为被烷基或芳基取代的膦,经由亚芳基或亚烷基桥接的被烷基或芳基取代的多齿膦,氮杂环卡宾,环戊二烯基和五甲基环戊二烯基,芳基,烯烃配体,氢化物,卤化物,羧酸化物,烷氧基化物,羰基,氢氧化物,三烷基胺,二烷基胺,单烷基胺,氮芳烃如吡啶或吡咯烷以及多齿胺。该有机金属配合物可以包含一种或多种不同的所述配体。
优选的配体是(单齿)膦或(多齿)聚膦,例如二膦,其具有至少一个具有1-20个,优选1-12个碳原子的未支化或支化的、无环或环状脂族、芳族或芳脂族基团。支化的脂环族和芳脂族基团的实例是-CH2-C6H11和-CH2-C6H5。可以作为举例提到的合适基团为甲基、乙基、1-丙基、2-丙基、1-丁基、2-丁基、1-(2-甲基)丙基、2-(2-甲基)丙基、1-戊基、1-己基、1-庚基、1-辛基、1-壬基、1-癸基、1-十一烷基、1-十二烷基、环戊烯基、环己基、环庚基和环辛基、甲基环戊基、甲基环己基、1-(2-甲基)戊基、1-(2-乙基)己基、1-(2-丙基庚基)、金刚烷基和降冰片基、苯基、甲苯基和二甲苯基以及1-苯基吡咯、1-(2-甲氧基苯基)吡咯、1-(2,4,6-三甲基苯基)咪唑和1-苯基吲哚。膦基可以包含两个或三个所述未支化或支化的、无环或环状脂族、芳族或芳脂族基团。这些可以相同或不同。
优选在步骤(a)中的该均相催化剂包含单齿或多齿膦配体,后者包含具有1-12个碳原子的未支化、无环或环状脂族基团或芳脂族基团或金刚烷基或1-苯基吡咯作为基团。
在所述未支化或支化的、无环或环状脂族、芳族或芳脂族基团中,各碳原子也可以被其他膦基取代。因此还包括多齿,例如二-或三齿膦配体,其膦基通过亚烷基或亚芳基桥接。膦基优选通过1,2-亚苯基、亚甲基、1,2-亚乙基、1,2-二甲基-1,2-亚乙基、1,3-亚丙基、1,4-亚丁基和1,5-亚丙基桥桥接。
特别合适的单齿膦配体是三苯基膦、三甲苯基膦、三正丁基膦、三正辛基膦、三甲基膦和三乙基膦,以及还有二(1-金刚烷基)-正丁基膦、二(1-金刚烷基)苄基膦、2-(二环己基膦基)-1-苯基-1H-吡咯、2-(二环己基膦基)-1-(2,4,6-三甲基苯基)-1H-咪唑、2-(二环己基膦基)-1-苯基吲哚、2-(二叔丁基膦基)-1-苯基吲哚、2-(二环己基膦基)-1-(2-甲氧基苯基)-1H-吡咯、2-(二叔丁基膦基)-1-(2-甲氧基苯基)-1H-吡咯和2-(二叔丁基膦基)-1-苯基-1H-吡咯。非常特别优选三苯基膦、三甲苯基膦、三正丁基膦、三正辛基膦、三甲基膦和三乙基膦,以及还有二(1-金刚烷基)-正丁基膦、2-(二环己基膦基)-1-苯基-1H-吡咯和2-(二叔丁基膦基)-1-苯基-1H-吡咯。
特别合适的多齿膦配体是二(二苯基膦基)甲烷、1,2-二(二苯基膦基)乙烷、1,2-二甲基-1,2-二(二苯基膦基)乙烷、1,2-二(二环己基膦基)乙烷、1,2-二(二乙基膦基)乙烷、1,3-二(二苯基膦基)丙烷、1,4-二(二苯基膦基)丁烷、2,3-二(二苯基膦基)丁烷、1,3-二(二苯基膦基)丙烷、1,1,1-三(二苯基膦基甲基)乙烷、1,1'-二(二苯基膦基)二茂铁和4,5-二(二苯基膦基)-9,9-二甲基氧杂蒽。
此外,优选可以提到氮杂环卡宾作为特别适合步骤(a)中的催化剂的配体。就此而言非常优选那些与Ru形成水溶性配合物的配体。特别优选1-丁基-3-甲基咪唑啉-2-亚基、1-乙基-3-甲基咪唑啉-2-亚基、1-甲基咪唑啉-2-亚基和二丙基咪唑啉-2-亚基。
可以提到的特别适合步骤(a)中的催化剂的配体还有环戊二烯基及其被烷基、芳基和/或羟基单-至五取代的衍生物,例如甲基环戊二烯基、五甲基环戊二烯基、四苯基羟基环戊二烯基和五苯基环戊二烯基。其他特别合适的配体是茚基及其如对环戊二烯基所述被取代的衍生物。
同样特别适合步骤(a)中的催化剂的配体是氢氧化物、氯化物、氢化物和羰基。
步骤(a)中的该过渡金属配合物催化剂当然可以包含两种或更多种如上所述的相同或不同配体。
均相催化剂可以直接以其活性形式使用或者可以在加入相应配体,优选上述单-或多齿膦配体或上述氮杂环卡宾下仅在反应条件下由常规标准配合物开始生产,所述配合物例如为[Ru(对异丙基苯甲烷)Cl2]2、[Ru(苯)Cl2]n、[Ru(CO)2Cl2]n、[Ru(CO)3Cl2]2、[Ru(COD)(烯丙基)]、[RuCl3*H2O]、[Ru(乙酰丙酮化物)3]、[Ru(DMSO)4Cl2]、[Ru(PPh3)3(CO)(H)Cl]、[Ru(PPh3)3(CO)Cl2]、[Ru(PPh3)3(CO)(H)2]、[Ru(PPh3)3Cl2]、[Ru(环戊二烯基)(PPh3)2Cl]、[Ru(环戊二烯基)(CO)2Cl]、[Ru(环戊二烯基)(CO)2H]、[Ru(环戊二烯基)(CO)2]2、[Ru(五甲基环戊二烯基)(CO)2Cl]、[Ru(五甲基环戊二烯基)(CO)2H]、[Ru(五甲基环戊二烯基)(CO)2]2、[Ru(茚基)(CO)2Cl]、[Ru(茚基)(CO)2H]、[Ru(茚基)(CO)2]2、二茂钌、[Ru(binap)Cl2]、[Ru(联吡啶)2Cl2*2H2O]、[Ru(COD)Cl2]2、[Ru(五甲基环戊二烯基)(COD)Cl]、[Ru3(CO)12]、[Ru(四苯基羟基-环戊二烯基)(CO)2H]、[Ru(PMe3)4(H)2]、[Ru(PEt3)4(H)2]、[Ru(PnPr3)4(H)2]、[Ru(PnBu3)4(H)2]、[Ru(三正辛基膦)4(H)2]、[IrCl3*H2O]、KIrCl4、K3IrCl6、[Ir(COD)Cl]2、[Ir(环辛烯)2Cl]2、[Ir(乙烯)2Cl]2、[Ir(环戊二烯基)Cl2]2、[Ir(五甲基环戊二烯基)Cl2]2、[Ir(环戊二烯基)(CO)2]、[Ir(五甲基环戊二烯基)(CO)2]、[Ir(PPh3)2(CO)(H)]、[Ir(PPh3)2(CO)(Cl)]、[Ir(PPh3)3(Cl)]。
步骤(a)中的该催化剂中金属组分,优选钌或铱的量通常为0.1-5000重量ppm,在每种情况下基于整个液体反应混合物。
在步骤(a)中的本发明方法可以在溶剂中或在没有溶剂下进行。本发明方法当然还可以在溶剂混合物中进行。
若步骤(a)中的反应在没有溶剂下进行,则在反应之后,尤其是在冷却至环境温度之后以及任选在步骤(a)之后加入溶剂或溶剂混合物之后,存在非极性相和极性水相。在反应之后,该均相催化剂优选以溶解形式存在于该极性相中,而产物存在于该非极性相中。若该催化剂在极性相中,则可以通过相分离将其从产物分离出来。若该催化剂部分或完全存在于非极性相中,则它可以保留在产物中或者可以通过用合适溶剂任选多次萃取而从中除去。所用萃取剂优选为强极性溶剂,其在通过蒸发浓缩之后可以任选与被萃取的催化剂一起再次用于该反应。合适的萃取剂例如为水、甲醇、乙醇、二甲亚砜、二甲基甲酰胺、离子液体如1-乙基-3-甲基咪唑硫酸氢盐或1-丁基-3-甲基咪唑甲基磺酸盐。还可以使用合适的吸收剂材料除去该催化剂。若该反应在与水和/或离子液体不溶混的溶剂中进行,则分离也可以通过将水或离子液体加入产物相中而进行。若就此而言该催化剂优先溶于水或该离子液体中,则可以用该溶剂将其从有机产物相中分离出来并且任选可以再利用。这可以通过选择合适配体而进行。
若步骤(a)中的反应在溶剂中进行,则通常选择溶剂量以使得仅原料(i)和(ii)溶于该溶剂中。溶剂量与原料(i)和(ii)的量的重量比通常为100:1-0.1:1,优选10:1-0.1:1。
若步骤(a)中的反应在溶剂中进行,则该溶剂可以与产物溶混并且可以在反应之后通过蒸馏分离出来。合适的溶剂例如为甲苯、苯、二甲苯,链烷烃,例如己烷、庚烷或辛烷,无环和环状醚如乙醚或四氢呋喃,以及还有具有不止3个碳原子的醇,其中OH基团与叔碳原子键合,例如叔戊基醇。优选苯、甲苯、二甲苯类、链烷烃、无环和环状醚或具有不止3个碳原子的醇,其中OH基团与叔碳原子键合,特别优选甲苯和叔戊基醇。在蒸馏过程中还可以分离出未反应原料,尤其是非极性原料。
在步骤(a)中还可以使用与产物或原料具有溶混隙的溶剂。作为适当选择配体的结果,该催化剂优先溶解于极性相中。此时合适的溶剂例如为水,亚砜如二甲亚砜,甲酰胺类如二甲基甲酰胺,离子液体如1-乙基-3-甲基咪唑硫酸氢盐和1-丁基-3-甲基咪唑甲基磺酸盐,优选水和离子液体。
若存在的话,步骤(a)中的溶剂也可以在反应条件下与原料和产物以及极性相如水或离子液体溶混且仅在冷却之后形成包含产物的第二液相。大部分催化剂溶于极性相中。此外,该相还可以包含一定比例的原料。然后可以将该催化剂与极性相一起分离出来并可以再利用。存在于产物中的催化剂级分随后可以通过萃取分离出来,合适的吸收剂材料如聚丙烯酸及其盐、磺化聚苯乙烯及其盐、活性炭、蒙脱土、膨润土以及还有沸石或其他材料可以留在产物中。
在步骤(a)中两相反应程序的方案情况下,合适的非极性溶剂尤其是甲苯、苯、二甲苯类,链烷烃,如己烷、庚烷和辛烷,其与该过渡金属催化剂上的极性或亲水性配体如氮杂环卡宾、极性磷烷或阳离子或阴离子配体组合,结果该过渡金属催化剂积聚在极性相中。在其中溶剂与产物形成非极性相且催化剂以及任选还有未反应原料与反应水和任选在反应后加入的其他溶剂形成极性相的该方案中,大部分催化剂和任选未反应原料可以通过简单相分离从产物相中分离出来并且可以再利用。
若挥发性副产物或未反应原料或加入的溶剂是不希望的,则这些可以通过蒸馏从产物中无问题地分离出来。
在另一方案中,步骤(a)中的反应在极性溶剂、水或离子液体中进行。产物可以通过加入溶解该产物但与用于反应的溶剂不溶混的非极性溶剂而分离出来。该非极性溶剂的实例是甲苯、苯,链烷烃,如己烷、庚烷或辛烷,以及无环或环状醚,如乙醚或四氢呋喃。若该催化剂优先溶解于极性相中,则可以用该溶剂将其从非极性产物相中分离出来并且任选可以再利用。
本发明步骤(a)中的反应在液相中在通常为20-250℃的温度下进行。优选该温度为至少100℃且优选至多200℃。该反应可以在0.1-25MPa绝对的总压下进行,该总压可以是氢气的压力与该溶剂在反应温度下的固有压力组合或者是气体如氮气或氩气与氢气组合的压力。平均反应时间通常为15分钟至100小时。
在本发明方法的优选实施方案中,在步骤(a)中在反应或聚亚烷基多胺制备过程中通过均相催化醇胺化分离出反应水。这意味着在通过在每种情况下在均相催化剂存在下使(i)脂族氨基醇在消除水下相互反应或(ii)脂族二胺或多胺与脂族二醇或多元醇在消除水下反应而制备聚亚烷基多胺的步骤(a)的方法过程中分离出反应水。反应水的额外除去就此而言也可以在制备该聚亚烷基多胺之后进行。
也可能有利的是连续从反应混合物中除去反应过程中形成的水。反应的水可以通过蒸馏从反应混合物中直接分离出来或者在加入合适的溶剂(夹带剂)下使用水分离器作为共沸物分离出来,或者可以通过加入吸水助剂而除去。
在步骤(a)中加入碱可能对产物形成具有积极影响。在这里可以提到的合适碱是碱金属氢氧化物、碱土金属氢氧化物、碱金属醇盐、碱土金属醇盐、碱金属碳酸盐和碱土金属碳酸盐,基于所用金属催化剂可以使用0.01-100当量碱。
在本发明方法的优选实施方案中,在步骤(a)中原料(i)脂族氨基醇、(ii)脂族二胺或多胺或脂族二醇或多元醇之一的杂原子O或N位于碳原子链上的α和β位且因此位于相邻碳原子上。
在本发明方法的优选实施方案中,在步骤(a)中原料(i)脂族氨基醇、(ii)脂族二胺或多胺或脂族二醇或多元醇之一的杂原子O或N位于碳原子链上的α和ω位且因此位于碳原子链的相对端。
在本发明方法的优选实施方案中,在步骤(a)中聚亚烷基多胺可以在氢气存在下得到。
氢气可以在连续或不连续从该体系中分离出反应水的同时注入。
在步骤(a)中由所述方法得到的聚亚烷基多胺在与氧化烯在步骤(b)中反应之前可以首先分离,或者与氧化烯在步骤(b)中的反应直接用来自步骤(a)的反应溶液进行。
在步骤(a)中由所述方法得到的聚亚烷基多胺进一步在本发明方法的步骤(b)中通过与氧化烯反应而改性。在该方法中,伯或仲氨基可能与环氧化物发生开环反应。烷氧基化胺的制备例如描述于H.L.Sanders等,Journal of the American Oil ChemistsSociety,1969,46,167-170中。胺和多胺的烷氧基化通常以两步进行:首先,氧化烯的用量应使得每个NH官能团的平均烷氧基化程度为0.5-1.5mol,优选0.75-1.25mol氧化烯。该步骤通常在作为溶剂的水中进行。
聚氧化烯链的进一步增长在除去溶剂,尤其是水之后在碱催化下进行。所用碱性催化剂例如为氢氧化钾、氢氧化钠、甲醇钾或甲醇钠,优选氢氧化钾、氢氧化钠。
步骤(b)中的氧化烯通常包含两个或更多个碳原子,优选2-20个碳原子,尤其是2-12个碳原子。
当使用不同氧化烯时,聚氧化烯链的增长可以以嵌段形式或者无规进行。
例如形成下列结构:
若该聚亚烷基多胺还带有羟基官能团,则这些优选同样在碱催化反应过程中在第二步骤中被氧化烯烷氧基化,例如正如下列方案所示:
步骤(b)中所用氧化烯优选为氧化乙烯、氧化丙烯、1,2-氧化丁烯、2,3-氧化丁烯、氧化戊烯、氧化己烷、氧化十二碳烯(R1=H、C1-C18烷基、芳基)。烷氧基化程度在这里通常为0.5-100个氧化烯单元/NH,优选1-50,特别优选5-25/NH。
本发明进一步提供了烷氧基化聚亚烷基多胺,优选烷氧基化聚亚乙基胺或烷氧基化聚亚丙基胺,它们通过包括步骤(a)和(b)的本发明方法的所述实施方案制备。
本发明进一步提供了通式(I)-(V)的烷氧基化聚亚烷基多胺或包含通式(I)-(V)的结构的烷氧基化聚亚烷基多胺:
其中
R相互独立地相同或不同且为H、C1-C50烷基,
R1相互独立地相同或不同且为H、C1-C18烷基、芳基,
l、m相互独立地相同或不同且为1-50,优选1-30,特别优选1-20的整数,n、k相互独立地相同或不同且为0-50,优选0-30,特别优选0-20的整数,i为3-50000的整数,
p、q相互独立地相同或不同且为0-100,优选1-50,特别优选5-25的整数。
本发明还涉及该烷氧基化聚亚烷基多胺的用途。
烷氧基化多胺如烷氧基化聚乙烯亚胺例如广泛用作a)洗涤添加剂,b)分散剂,c)织物助剂。烷氧基化聚乙烯亚胺的用途例如描述于专利说明书US4891260、US4647921、US4654043和US4645611中。
本发明进一步提供了一种制备烷氧基化聚亚烷基多胺的方法,其中使通式(I’)-(III’)的聚亚烷基多胺或包含通式(I’)-(III’)的结构的聚亚烷基多胺与氧化烯反应而得到烷氧基化聚亚烷基多胺:
其中
R相互独立地相同或不同且为H、C1-C50烷基,
l、m相互独立地相同或不同且为1-50,优选1-30,特别优选1-20的整数,n、k相互独立地相同或不同且为0-50,优选0-30,特别优选0-20的整数,i为3-50000的整数。
本发明进一步提供了制备烷氧基化聚亚烷基多胺的方法,其中不使用氮丙啶,不形成不希望的联产物且得到具有所需链长的产物。
本发明通过实施例更详细说明本发明,这些实施例不限制本发明主题。实施例
伯胺、仲胺和叔胺的含量(mg KOH/g胺)按照ASTM D2074-07测定。
OH值按照DIN53240测定。
碱值通过按照ASTM D4739-11用盐酸电势滴定测定。
胺值按照DIN53176测定。
实施例1
在90℃下将131.2g乙醇胺和二亚乙基胺的聚亚烷基多胺—包含102mg KOH/g伯胺、563mg KOH/g仲胺和76mg KOH/g叔胺—作为初始料引入含有6.6g水的高压釜中。将该反应器用氮气冲洗几次并将温度提高到120℃。在该温度下计量加入78.9g氧化乙烯并将该混合物后搅拌2小时。在冷却至80℃之后加入6.3g氢氧化钾水溶液(50%浓度)并将该混合物在真空下于120℃下脱水。用氮气提升真空并将温度提高到140℃。在140℃下在7小时内计量加入710.3g氧化乙烯。然后将该混合物后搅拌5小时。将反应混合物冷却至80℃并真空除去挥发性成分。这得到930.0g褐色粘稠油(OH值=226.4mg KOH/g,碱值=61.9mg KOH/g,胺值=109.4mgKOH/g)。根据1H-NMR,该组成对应于具有10个EO单元/NH的聚亚烷基多胺。
实施例2
在90℃下将161.4g1,2-戊二醇和1,3-丙二胺的聚亚烷基多胺—包含180mg KOH/g伯胺、304mg KOH/g仲胺和34mg KOH/g叔胺—作为初始料引入含有8.0g水的高压釜中。将该反应器用氮气冲洗几次并将温度提高到100℃。在该温度下计量加入84.0g氧化乙烯并将该混合物后搅拌1小时。在真空除去挥发性成分之后得到227g褐色油(OH值:496.5mg KOH/g)。
将134.9g该油作为初始料与0.8g叔丁醇钾引入高压釜中。在130℃下将该反应器用氮气冲洗几次并在该温度下注入262.6g氧化乙烯。在后搅拌1小时之后真空除去挥发性成分并分离390g深褐色油,其可溶于水中得到透明溶液。根据1H-NMR,该组成对应于1,3-丙二胺+1,2-戊二醇+5EO/OH的低聚物。
将303.3g该油和1.2g叔丁醇钾作为初始料引入高压釜中并在130℃下用氮气惰性化几次。在130℃下在3小时内计量加入601.1g氧化乙烯。在130℃下搅拌2小时后真空除去挥发性成分并分离900.3g褐色固体(OH值:115.5mg KOH/g,总胺:42.6mg KOH/g,叔胺:5.6mg KOH/g,碱值:37.6mg KOH/g)。该组成对应于1,3-丙二胺+1,2-戊二醇+20EO/OH的低聚物。
Claims (18)
1.一种制备烷氧基化聚亚烷基多胺的方法,包括下列步骤:
a)均相催化醇胺化,其中在均相催化剂存在下在消除水下
(i)使脂族氨基醇相互反应,或者
(ii)使脂族二胺或多胺与脂族二醇或多元醇反应,
得到聚亚烷基多胺,
b)使这些聚亚烷基多胺与氧化烯反应而得到烷氧基化聚亚烷基多胺,
其中所述催化剂包含单齿或多齿膦配体。
2.根据权利要求1的方法,其中在步骤a)中的反应之后存在得到至少一个非极性相和至少一个极性相的相分离。
3.根据权利要求1的方法,其中所述催化剂为过渡金属配合物催化剂。
4.根据权利要求2的方法,其中所述催化剂为过渡金属配合物催化剂。
5.根据权利要求1-4中任一项的方法,其中所述催化剂包含氮杂环卡宾配体。
6.根据权利要求1-4中任一项的方法,其中所述催化剂包含选自环戊二烯基、取代环戊二烯基、茚基和取代茚基的配体。
7.根据权利要求1-4中任一项的方法,其中所述催化剂包含选自氢氧化物、氢化物、羰基和氯化物的配体。
8.根据权利要求1-4中任一项的方法,其中所述反应在溶剂或溶剂混合物存在下进行。
9.根据权利要求1-4中任一项的方法,其中在步骤a)中反应水在通过均相催化醇胺化制备聚亚烷基多胺的过程中分离出来。
10.根据权利要求1-4中任一项的方法,其中步骤a)在氢气存在下进行。
11.根据权利要求1-4中任一项的方法,其中步骤b)中的氧化烯包含两个或更多个碳原子。
12.一种通式(I)-(V)的烷氧基化聚亚烷基多胺:
其中
R相互独立地相同或不同且为H、C1-C50烷基,
R1相互独立地相同或不同且为H、C1-C18烷基、芳基,
l、m相互独立地相同或不同且为1-50的整数,
n、k相互独立地相同或不同且为0-50的整数,
i为3-50 000的整数,
p、q相互独立地相同或不同且为0-100的整数。
13.根据权利要求12的烷氧基化聚亚烷基多胺,其中l、m相互独立地相同或不同且为1-30的整数,n、k相互独立地相同或不同且为0-30的整数,p、q相互独立地相同或不同且为1-50的整数。
14.根据权利要求12的烷氧基化聚亚烷基多胺,其中l、m相互独立地相同或不同且为1-20的整数,n、k相互独立地相同或不同且为0-20的整数,p、q相互独立地相同或不同且为5-25的整数。
15.根据权利要求12-14中任一项的烷氧基化聚亚烷基多胺的用途,作为
a)洗涤添加剂,
b)分散剂,
c)织物助剂,
d)木材保护剂,
e)腐蚀抑制剂。
16.一种制备烷氧基化聚亚烷基多胺的方法,其中使通式(I’)-(III’)的聚亚烷基多胺与氧化烯反应而得到烷氧基化聚亚烷基多胺:
其中
R相互独立地相同或不同且为H、C1-C50烷基,
l、m相互独立地相同或不同且为1-50的整数,
n、k相互独立地相同或不同且为0-50的整数,
i为3-50 000的整数,
在均相催化剂存在下得到通式(I’)-(III’)的聚亚烷基多胺,其中所述催化剂为包含钌或铱的过渡金属配合物催化剂。
17.根据权利要求16的方法,其中l、m相互独立地相同或不同且为1-30的整数,n、k相互独立地相同或不同且为0-30的整数。
18.根据权利要求16的方法,其中l、m相互独立地相同或不同且为1-20的整数,n、k相互独立地相同或不同且为0-20的整数。
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JP6042446B2 (ja) * | 2011-11-25 | 2016-12-14 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | アルコールの均一系接触アミノ化によるポリアルキレンポリアミンの分子量増大 |
MX2015013806A (es) | 2013-03-28 | 2016-06-02 | Basf Se | Polieteraminas a base de 1,3-dialcoholes. |
EP2842936A1 (en) | 2013-08-26 | 2015-03-04 | Basf Se | Etheramines based on alkoxylated glycerine or trimethylolpropane. |
MX2016002583A (es) | 2013-08-26 | 2016-10-26 | Basf Se | Polietilenimina alcoxilada con un bajo punto de fusion. |
WO2015091160A1 (en) | 2013-12-16 | 2015-06-25 | Basf Se | Modified polysaccharide for use in laundry detergent and for use as anti-greying agent |
KR20170126471A (ko) * | 2015-02-25 | 2017-11-17 | 바스프 에스이 | 오염된 금속 표면의 세정 방법 및 상기 방법에 유용한 성분 |
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US11130923B2 (en) | 2017-04-11 | 2021-09-28 | Basf Se | Alkoxylated amines as fuel additives |
WO2021204758A1 (en) | 2020-04-07 | 2021-10-14 | Basf Se | Polymer composition, which is suitable as anti-greying agent in detergent formulations |
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US11906576B1 (en) | 2021-05-04 | 2024-02-20 | Johnstech International Corporation | Contact assembly array and testing system having contact assembly array |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4505839A (en) * | 1981-05-18 | 1985-03-19 | Petrolite Corporation | Polyalkanolamines |
US4888425A (en) * | 1982-04-30 | 1989-12-19 | Union Carbide Chemicals And Plastics Company Inc. | Preparation of polyalkylene polyamines |
CN1102668A (zh) * | 1985-03-14 | 1995-05-17 | 鲁布里佐尔公司 | 制备润滑剂组合物分散剂的方法 |
WO1997023546A1 (en) * | 1995-12-21 | 1997-07-03 | The Procter & Gamble Company | A process for ethoxylating polyamines |
CN101965219A (zh) * | 2008-03-04 | 2011-02-02 | 巴斯夫欧洲公司 | 烷氧基化聚链烷醇胺用于使油-水乳液破乳的用途 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3708539A (en) | 1970-02-06 | 1973-01-02 | Union Oil Co | Condensation of ammonia or a primary or secondary amine with an alcohol |
EP0034480A3 (en) | 1980-02-14 | 1982-01-13 | Grigg, Ronald Ernest | Alkylation of amines |
CA1228449A (en) * | 1982-04-30 | 1987-10-20 | William B. Herdle | Preparation of polyalkylene polyamines |
DE3400989A1 (de) | 1984-01-13 | 1985-07-18 | Basf Ag, 6700 Ludwigshafen | Verfahren zum entschlichten von baumwolle und baumwollhaltigen geweben |
GB8402801D0 (en) | 1984-02-02 | 1984-03-07 | Ici Plc | Dispersion |
US4647921A (en) | 1984-03-12 | 1987-03-03 | Otis Elevator Company | Alphanumeric display |
ATE37355T1 (de) * | 1984-07-25 | 1988-10-15 | Air Prod & Chem | Selektive synthese von substituierten aminen. |
US4745190A (en) | 1984-07-25 | 1988-05-17 | Air Products And Chemicals, Inc. | Selective synthesis of substituted amines |
US4891260A (en) | 1987-12-03 | 1990-01-02 | Pelikan Aktiengesellschaft | Multilayer flexible transfer ribbon |
DE4136661A1 (de) * | 1991-11-07 | 1993-05-13 | Basf Ag | Erdoelemulsionsspalter |
JP2011503284A (ja) * | 2007-11-09 | 2011-01-27 | ザ プロクター アンド ギャンブル カンパニー | アルコキシル化ポリアルカノールアミンを有する洗浄組成物 |
ES2477238T3 (es) * | 2010-05-31 | 2014-07-16 | Basf Se | Polialquilenpoliaminas por aminaci�n de alcohol catalizada homog�neamente |
US8697834B2 (en) | 2010-05-31 | 2014-04-15 | Basf Se | Polyalkylenepolyamines by homogeneously catalyzed alcohol amination |
US8637709B2 (en) | 2011-03-08 | 2014-01-28 | Basf Se | Process for the preparation of primary amines by homogeneously catalyzed alcohol amination |
US8785693B2 (en) | 2011-03-08 | 2014-07-22 | Basf Se | Process for the preparation of primary amines by homogeneously catalyzed alcohol amination |
US9193666B2 (en) | 2011-03-08 | 2015-11-24 | Basf Se | Process for preparing alkanolamines by homogeneously catalyzed alcohol amination |
US8912361B2 (en) | 2011-03-08 | 2014-12-16 | Basf Se | Process for preparing di-, tri- and polyamines by homogeneously catalyzed alcohol amination |
US8877977B2 (en) | 2011-11-25 | 2014-11-04 | Basf Se | Synthesis of polyalkylenepolyamines having a low color index by homogeneously catalyzed alcohol amination in the presence of hydrogen |
-
2012
- 2012-11-19 CN CN201280057887.7A patent/CN103958567B/zh not_active Expired - Fee Related
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- 2012-11-19 ES ES12788519.2T patent/ES2590146T3/es active Active
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4505839A (en) * | 1981-05-18 | 1985-03-19 | Petrolite Corporation | Polyalkanolamines |
US4888425A (en) * | 1982-04-30 | 1989-12-19 | Union Carbide Chemicals And Plastics Company Inc. | Preparation of polyalkylene polyamines |
CN1102668A (zh) * | 1985-03-14 | 1995-05-17 | 鲁布里佐尔公司 | 制备润滑剂组合物分散剂的方法 |
WO1997023546A1 (en) * | 1995-12-21 | 1997-07-03 | The Procter & Gamble Company | A process for ethoxylating polyamines |
CN101965219A (zh) * | 2008-03-04 | 2011-02-02 | 巴斯夫欧洲公司 | 烷氧基化聚链烷醇胺用于使油-水乳液破乳的用途 |
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