CN1325436A - 漂白和氧化催化剂 - Google Patents
漂白和氧化催化剂 Download PDFInfo
- Publication number
- CN1325436A CN1325436A CN99813089A CN99813089A CN1325436A CN 1325436 A CN1325436 A CN 1325436A CN 99813089 A CN99813089 A CN 99813089A CN 99813089 A CN99813089 A CN 99813089A CN 1325436 A CN1325436 A CN 1325436A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- methyl
- ligand
- diamines
- alkyl
- 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.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- -1 metal complex compounds Chemical class 0.000 claims abstract description 90
- 239000003446 ligand Substances 0.000 claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 100
- 239000000203 mixture Substances 0.000 claims description 80
- 238000004061 bleaching Methods 0.000 claims description 58
- 239000003599 detergent Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 125000001118 alkylidene group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 18
- 239000004744 fabric Substances 0.000 abstract description 9
- 150000004696 coordination complex Chemical class 0.000 abstract description 8
- 150000004699 copper complex Chemical class 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 238000010189 synthetic method Methods 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 23
- 238000005481 NMR spectroscopy Methods 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 235000019439 ethyl acetate Nutrition 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 8
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical class [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ACDAPUOXXWLLSC-UHFFFAOYSA-N (3-methylpyridin-2-yl)methanol Chemical compound CC1=CC=CN=C1CO ACDAPUOXXWLLSC-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- HYOBIUULDPLKIE-UHFFFAOYSA-N (5-methylpyridin-2-yl)methanol Chemical compound CC1=CC=C(CO)N=C1 HYOBIUULDPLKIE-UHFFFAOYSA-N 0.000 description 4
- OJUIRUMDLUMSTN-UHFFFAOYSA-N 2-(benzylamino)acetonitrile;hydrochloride Chemical compound Cl.N#CCNCC1=CC=CC=C1 OJUIRUMDLUMSTN-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000023 Kugelrohr distillation Methods 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- BNUZCVIMDLJKGA-UHFFFAOYSA-N (3,5-dimethylpyridin-2-yl) acetate Chemical compound CC(=O)Oc1ncc(C)cc1C BNUZCVIMDLJKGA-UHFFFAOYSA-N 0.000 description 3
- LIRQOUKPZWQBRE-UHFFFAOYSA-N (5-ethylpyridin-2-yl)methanol Chemical compound CCC1=CC=C(CO)N=C1 LIRQOUKPZWQBRE-UHFFFAOYSA-N 0.000 description 3
- RRIYNYAKRPUOBF-UHFFFAOYSA-N (5-ethylpyridin-2-yl)methyl acetate Chemical compound CCC1=CC=C(COC(C)=O)N=C1 RRIYNYAKRPUOBF-UHFFFAOYSA-N 0.000 description 3
- VXAOLDZFARINGE-UHFFFAOYSA-N 2-(ethylamino)acetonitrile Chemical compound CCNCC#N VXAOLDZFARINGE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229940077388 benzenesulfonate Drugs 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 150000004698 iron complex Chemical class 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 230000005298 paramagnetic effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- YXTJJTICRTWVLE-UHFFFAOYSA-N (3,4-dimethylpyridin-2-yl) acetate Chemical compound C(C)(=O)OC1=NC=CC(=C1C)C YXTJJTICRTWVLE-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- 108010025188 Alcohol oxidase Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical compound [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical compound COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 description 1
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- RJTZQPTVNWCDBI-UHFFFAOYSA-N n,n'-bis(pyridin-2-ylmethyl)ethane-1,2-diamine Chemical compound C=1C=CC=NC=1CNCCNCC1=CC=CC=N1 RJTZQPTVNWCDBI-UHFFFAOYSA-N 0.000 description 1
- SVEUVITYHIHZQE-UHFFFAOYSA-N n-methylpyridin-2-amine Chemical compound CNC1=CC=CC=N1 SVEUVITYHIHZQE-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000003217 pyrazoles Chemical class 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
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- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical group [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明提供了含有包括特殊五齿含N配位体的催化活性铁、锰或铜配合物的漂白氧化催化剂。金属配合物可活化过氧化氢或过氧酸,提供良好的去污性质。此外,获得了在碱性含水环境中这些金属配合物化合物的明显改善的稳定性,尤其是在通常存在于织物洗涤母液中的过氧化合物的浓度下。
Description
发明领域
本发明涉及漂白和氧化催化剂、含有该催化剂的组合物,尤其是漂白和洗涤剂漂白组合物和使用该催化剂漂白和洗涤载污体,尤其是织物载污体的方法。更具体地说,本发明涉及含有与过氧漂白剂一起使用的含有与铁、锰或铜离子配位的五齿配位体的催化配合物。
发明背景
许多年来人们已知过氧漂白剂,并用于各种工业和家庭漂白和洗涤过程,然而,该试剂的活性是极其依赖于温度的,在低于60℃的温度下急剧下降。尤其对于洗涤织物,高温操作是经济上不合乎需要的和事实上不利的。
解决该问题的一种尝试是附加使用所谓的漂白活性剂,也称为漂白前体,这些活性剂通常是羧酸酯,它们与过氧化氢阴离子在水溶液中反应产生相应的过氧酸,从而氧化载污体。然而,这些活性剂是非催化的,一旦活性剂被过水解,它不再能够循环,因此,通常需要使用相对高含量的活性剂,由于漂白活性剂相当昂贵,在该含量下使用活性剂的成本将是禁止性的。
另一种尝试是使用过渡金属配合物作为催化剂以活化过氧漂白剂,例如US-A-4728455公开了使用具有高水解和氧化稳定性的锰(Ⅲ)-葡萄糖酸盐作为过氧化物漂白催化剂。在EP-A-0458379中,公开了例如三氮杂环壬烷基锰配合物,在低温下它显示了高的催化氧化活性,这尤其适用于漂白用途。
在WO-A-9534628中,公开了含有某些五齿含氮配位体,尤其是N,N-二(吡啶-2-基甲基)-二(吡啶-2-基)甲胺(“N4Py”)的铁配合物作为漂白和氧化催化剂的用途,产生良好漂白和氧化活性,然而配位体的合成是相当昂贵的。
WO-A-9718035公开了含有配位体,例如N,N’-二(吡啶-2-基甲基)乙-1,2-二胺(“Bispicen”)、N-甲基-N,N’,N’-三(吡啶-2-基甲基)乙-1,2-二胺(“TrispicMeen”)和N,N,N’,N’-四(吡啶-2-基甲基)乙-1,2-二胺(“TPEN”)的铁和锰配合物,它用作有机物质的过氧化物氧化催化剂。
WO-A-9748787涉及含有多齿配位体的铁配合物,它含有至少6个氮或氧杂原子,金属离子与至少5个杂原子配位,例如1,1,4,8,11,11-六(吡啶-2-基甲基)-1,4,8,11-四氮杂十一烷(“Hptu”),它用作过氧化物、过氧酸和分子氧漂白和氧化的催化剂。
尽管已知的过渡金属配合物在一定程度上已成功地用作漂白或氧化过程的催化剂,但人们仍需要其它的漂白和氧化催化剂,尤其在活性或成本方面更有效者。
现在我们惊奇地发现通过具有含有取代的杂芳基的五齿配位体的铁、锰或铜配合物可获得明显或改善的催化活性。此外,我们发现显示该活性的催化剂可通过可容易接受的合成方法制备。
发明概述
因此,一方面,本发明提供了含有通式(A)配合物的漂白和氧化催化剂:
[LMXn]zYq (A)其中
M表示Ⅱ、Ⅲ、Ⅳ或Ⅴ氧化态的铁、Ⅱ、Ⅲ、Ⅳ、Ⅵ或Ⅶ氧化态的锰或Ⅰ、Ⅱ或Ⅲ氧化态的铜;
X表示配位物质;
n表示零或0-3的整数;
z表示配合物的电荷,是整数,它可以是正数、零或负数;
Y表示抗衡离子,其类型取决于配合物的电荷;
q=z/[电荷Y];
L表示通式(B)的五齿配位体:
R1R1N-W-NR1R2 (B)其中每个R1分别表示-R3-V,其中R3表示选择性地取代的亚烷基、亚烯基、氧基亚烷基、氨基亚烷基或亚烷基醚,和V表示取代的选自吡啶基、吡嗪基、吡唑基、咪唑基、苯并咪唑基、嘧啶基、三唑基和噻唑基的杂芳基;
W表示选择性地取代的亚烷基桥基,其选自-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-和-CH2-C6H4-CH2-;
R2表示选自烷基、芳基和芳烷基的基团,它选择性地被选自羟基、烷氧基、羧酸盐、羧酰胺、羧酸酯、磺酸盐、胺、烷基胺和N+(R4)3的取代基取代,其中R4选自H、烷基、烯基、芳烷基、芳烯基、氧基烷基、氧基烯基、氨基烷基、氨基烯基、烷基醚和烯基醚。
另一方面,本发明提供了含有过氧漂白化合物和如上定义的催化剂的漂白组合物。过氧漂白化合物优选选自过氧化氢、释放或产生过氧化氢的化合物、过氧酸和它们的盐,和它们的混合物,漂白组合物还含有过氧酸漂白前体。
另一方面,本发明提供洗涤剂漂白组合物,其含有过氧漂白化合物和如上定义的催化剂、表面活性物质和洗涤剂助洗剂。
有利的是,本发明的配合物被发现在过氧化氢或过氧酸存在下提供良好的去污性。此外,还显示改善的漂白活性,尤其是在含有在织物洗涤周期中通常存在于洗涤母液中的浓度下的过氧化合物的碱性水溶液中。配合物还可提供有机物质,例如烯烃、醇和未活化的烃的改善的氧化作用。发明的详细描述
通常,本发明的金属配合物催化剂可用于含有过氧化合物,选择性地和其前体的漂白体系,它适用于载污体的洗涤和漂白,包括洗衣、餐具洗涤和硬表面清洁。此外,本发明的金属配合物催化剂可用于漂白纺织品、纸张和木浆工业以及废水处理。
如上所述,本发明的催化剂的优点是它们在过氧化合物存在下在碱性含水介质中显示明显高的氧化活性。
本发明的催化剂的第二个优点是它们比上述铁配合物能够在更宽的pH范围(通常pH6-11)下显示良好漂白活性。它们的性能在约10的pH下尤其改善。由于现存洗涤剂配方采用相当碱性的条件,以及在织物洗涤过程中pH由碱性(通常pH10)转变为更加中性的数值的趋势,该优点是尤其有益的。此外,在机械餐具洗涤配方中使用本发明的催化剂时,该优点是有益的。
另一优点是本发明的催化剂具有相对低的分子量,因此通常是非常重量-有效的。
本发明的活性金属配合物催化剂可以按定义明确的配合物配量。此外,催化剂可由催化剂的合适前体就地形成,例如在含有前体物质的溶液或分散液中。在该实例中,活性催化剂可在含有金属M的盐和配位体L或产生配位体L的物质在合适溶剂中的混合物中就地形成。因此,例如如果M是铁,铁盐,例如硝酸铁可在溶液中与配位体L或产生配位体L的物质混合以形成活性金属配合物。在另一实例中,配位体L或产生配位体L的物质可与存在于漂白或氧化基质中或洗涤母液中的金属M离子混合以就地形成活性催化剂。合适的产生配位体L的物质包括无金属化合物,或金属配位配合物,其含有配位体L,并可被金属M离子取代以形成式(A)的活性金属配合物。
因此,显然本发明的催化剂可通过任何合适的方法形成,包括就地形成,从而催化剂的前体在贮存或使用条件下转变成通式(A)的活性金属配合物。优选催化剂作为定义明确的配合物形成,或在含有金属M的盐和配位体L或产生配位体的物质的溶剂混合物中形成。
具有如上定义的通式R1R1N-W-NR1R2的配位体L是五齿配位体。本文中‘五齿配位体’是指在金属配合物中五个杂原子可与金属M配位,它的两个杂原子通过桥基W连接,在三个R1基团的每个中包含一个配位杂原子,优选配位杂原子是氮原子。
配位体L在三个R1基团的每一个中包含至少一个取代的杂芳基,取代的杂芳基优选是取代的吡啶-2-基,更优选在上述通式中经亚甲基基团连接于N原子的甲基-或乙基-取代的吡啶-2-基。取代的杂芳基更优选是经亚甲基连接于N原子的3-甲基-吡啶-2-基。
基团R2是取代或未取代的烷基、芳基或芳烷基,其条件是R2与上述通式中每个基团R1不同。合适的取代基选自羟基、烷氧基、羧酸盐、羧酰胺、羧酸酯、磺酸盐、胺、烷基胺和N+(R4)3,其中R4选自H、烷基、烯基、芳烷基、芳烯基、氧基烷基、氧基烯基、氨基烷基、氨基烯基、烷基醚和烯基醚。优选R2是甲基、乙基、苄基、2-羟基乙基或2-甲氧基乙基,R2更优选甲基或乙基。
桥基W可以是取代或未取代的亚烷基,其选自-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-和-CH2-C6H4-CH2-(其中-C6H4-可以是邻-、对-或间-C6H4-);桥基优选是亚乙基或1,4-亚丁基,更优选亚乙基。
以其最简单形式的优选配位体的实例是:N-甲基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-乙基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-苄基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-(2-羟基乙基)-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-(2-甲氧基乙基)-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-甲基-N,N’,N’-三(5-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-乙基-N,N’,N’-三(5-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-苄基-N,N’,N’-三(5-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-(2-羟基乙基)-N,N’,N’-三(5-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-(2-甲氧基乙基)-N,N’,N’-三(5-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-甲基-N,N’,N’-三(3-乙基-吡啶-2-基甲基)乙-1,2-二胺;N-乙基-N,N’,N’-三(3-乙基-吡啶-2-基甲基)乙-1,2-二胺;N-苄基-N,N’,N’-三(3-乙基-吡啶-2-基甲基)乙-1,2-二胺;N-(2-羟基乙基)-N,N’,N’-三(3-乙基-吡啶-2-基甲基)乙-1,2-二胺;N-(2-甲氧基乙基)-N,N’,N’-三(3-乙基-吡啶-2-基甲基)乙-1,2-二胺;N-甲基-N,N’,N’-三(5-乙基-吡啶-2-基甲基)乙-1,2-二胺;N-乙基-N,N’,N’-三(5-乙基-吡啶-2-基甲基)乙-1,2-二胺;N-苄基-N,N’,N’-三(5-乙基-吡啶-2-基甲基)乙-1,2-二胺;和N-(2-甲氧基乙基)-N,N’,N’-三(5-乙基-吡啶-2-基甲基)乙-1,2-二胺。
更优选的配位体是:N-甲基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-乙基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-苄基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;N-(2-羟基乙基)-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;和N-(2-甲氧基乙基)-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺。
最优选的配位体是:N-甲基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺;和N-乙基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺。
本发明的金属配合物催化剂可包括合适的抗衡离子以平衡在由配位体L、金属M和配位物质X形成的配合物的电荷z。因此,如果电荷z是正的,Y可以是阴离子,例如R6COO-、BPh4 -、ClO4 -、BF4 -、PF6 -、R6SO3 -、R6SO4 -、SO4 2-、NO3 -、F-、Cl-、Br-或I-,其中R6是H、选择性地取代的烷基或选择性地取代的芳基。如果z是负的,Y可以是通常的阳离子,例如碱金属、碱土金属或(烷基)铵阳离子。
合适的抗衡离子Y包括形成贮存稳定固体的物质,优选金属配合物的优选抗衡离子选自R6COO-、C1O4 -、BF4 -、PF6 -、R6SO3 -(尤其是CF3SO3 -)、R6SO4 -、SO4 2-、NO3 -、F-、Cl-、Br-和I-,其中R6是H、选择性地取代的苯基、萘基或C1-C4烷基。
合适的配位物质X可选自R5OH、NR5 3、R5CN、R5OO-、R5S-、R5O-、R5COO-、OCN-、SCN-、N3 -、CN-、F-、Cl-、Br-、I-、O2-、O2 2-、O2 -、NO3 -、NO2 -、SO4 2-、SO3 2-、PO4 3-和选自吡啶、吡嗪、吡唑、咪唑、苯并咪唑、嘧啶、三唑和噻唑的芳香N供体,其中R5选自H、选择性取代的烷基和选择性取代的芳基。X还可以是物质LMO-或LMOO-,其中M是过渡金属和L是如上定义的配位体。优选的配位物质X是CH3CN、H2O、F-、Cl-、Br-、OOH-、O2 2-、O2 -、LMO-、LMOO-、R5COO-和R5O-,其中R5表示H或选择性地取代的苯基、萘基或C1-C4烷基。
以在含水漂白溶液中金属M的每百万中的份数(ppm)表示的金属配合物催化剂的有效含量通常为0.001ppm-100ppm,优选0.01ppm-20ppm,最优选0.1ppm-10ppm,较高的含量是需要的,这应用于工业漂白过程,例如纺织品和纸浆漂白。较低范围含量优选用于家庭洗衣操作。
金属M可选自铁(Fe)、锰(Mn)和铜(Cu),优选金属是Fe或Mn,更优选Fe。过氧漂白化合物
过氧漂白化合物可以是在水溶液中产生过氧化氢的任何化合物,包括过氧化氢和过氧化氢加合物。过氧化氢源是现有技术中已知的,它们包括碱金属过氧化物、有机过氧化物,例如脲过氧化物和无机过盐,例如碱金属过硼酸盐、过碳酸盐、过磷酸盐、过硅酸盐和过硫酸盐,两种或多种该化合物的混合物也是合适的。
尤其优选过硼酸钠四水合物,尤其是过硼酸钠单水合物,由于其高活性氧含量,过硼酸钠单水合物是优选的,由于环境原因,也优选过碳酸钠。本发明的组合物中的含量通常为按重量计约2-35%,优选按重量计10-25%。
另一合适的过氧化氢产生体系是C1-C4链烷醇氧化酶和C1-C4链烷醇的组合,尤其是甲醇氧化酶(MOX)和乙醇的组合。该组合在WO-A-9507972中公开,列为本文参考文献。其它合适的过氧化氢产生体系使用葡萄糖氧化酶与葡萄糖的组合。
烷基羟基过氧化物是另一类合适的过氧漂白化合物,这些物质的实例包括枯烯氢过氧化物和叔丁基氢过氧化物。
有机过氧酸也适合用作过氧漂白化合物,该物质通常具有通式:其中R是含有1-约20个碳原子的亚烷基或烷基-或亚烷基(alkylidene)取代的亚烷基,它选择性地含有内在酰胺链;或亚苯基或取代的亚苯基;和Y是H、卤素、烷基、芳基、酰亚氨基-芳香或非芳基团、-COOH或-COOOH基团或季铵基团。
用于本文的典型单过氧酸包括,例如:(ⅰ)过氧苯甲酸和环取代的过氧苯甲酸,例如过氧-α-萘甲酸;(ⅱ)脂族、取代的脂族和芳基烷基单过氧酸,例如过氧月桂酸、过氧硬脂酸和N,N-邻苯二甲酰氨基过氧己酸(PAP);和(ⅲ)6-辛基氨基-6-氧代-过氧己酸。
用于本文的典型二过氧酸包括,例如:(ⅳ)1,12-二过氧十二烷二酸(DPDA);(ⅴ)1,9-二过氧壬二酸;(ⅵ)二过氧巴西基酸;二过氧癸二酸和二过氧间苯二甲酸;(ⅶ)2-癸基二过氧丁-1,4-二酸;和(ⅷ)4,4’-磺酰基二过氧苯甲酸。
同样合适的无机过氧酸化合物,例如单过硫酸钾(MPS)。如果有机或无机过氧酸用作过氧化合物,其数量通常为按重量计约2-10%,优选按重量计4-8%。
通常本发明的漂白组合物可合适地配制成含有按重量计2-35%,优选5-25%的过氧漂白化合物。
所有这些过氧化合物可单独地或与过氧酸漂白前体和/或不含过渡金属的有机漂白催化剂混合使用。
过氧酸漂白前体是已知的,在文献中充分描述,例如GB-A-0,836,988;GB-A-0,864,798;GB-A-0,907,356;GB-A-1,003,310和GB-A-1,519,351;DE-A-3,337,921;EP-A-0,185,522;EP-A-0,174,132;EP-A-0,120,591;和US-A-1,246,339;US-A-3,332,882;US-A-4,128,494;US-A-4,412,934和US-A-4,675,393
另一种有用的过氧酸漂白前体是在US-A-4751015和US-A-4397757、EP-A-0284292和EP-A-0331229中公开的阳离子物质,即季铵取代的过氧酸前体。这类过氧酸漂白前体的实例是:2-(N,N,N-三甲基铵)乙基钠-4-磺基苯基碳酸盐氯化物-(SPCC);N-辛基-N,N-二甲基-N10-碳苯氧基癸基氯化铵-(ODC);3-(N,N,N-三甲基铵)丙基钠-4-磺基苯基羧酸盐;和N,N,N-三甲基铵甲苯氧基苯磺酸盐。
其它种类的漂白前体如EP-A-0303520、EP-A-0458396和EP-A-0464880中公开通过阳离子腈形成。
任何一种这些过氧酸漂白前体可用于本发明中,虽然某些会比其它的更优选。在上述种类的漂白前体中,优选的种类是酯,包括酰基苯酚磺酸酯和酰基烷基苯酚磺酸酯;酰基酰胺;和季铵取代的过氧酸前体,包括阳离子腈。
优选过氧酸漂白前体或活性剂的实例是钠-4-苯甲酰基氧基苯磺酸盐(SBOBS);N,N,N’,N’-四乙酰基乙二胺(TAED);钠-1-甲基-2-苯甲酰基氧基苯-4-磺酸盐;钠-4-甲基-3-苯甲酰基氧基苯甲酸盐;2-(N,N,N-三甲基铵)乙基钠-4-磺基苯基碳酸盐氯化物(SPCC);甲苯酰氧基-苯磺酸三甲铵;壬酰氧基苯磺酸钠(SNOBS);3,5,5-三甲基己酰基-氧基苯磺酸钠(STHO BS);和取代的阳离子腈。
前体可以按组合物重量计至多12%,优选2-10%的数量使用。洗涤剂漂白组合物
本发明的漂白组合物在洗涤剂配方中具有特别的应用。因此,另一方面,本发明提供了含有如上定义的过氧漂白化合物、上述具有通式(A)的金属配合物催化剂、表面活性物质和洗涤助洗剂的洗涤剂漂白组合物。
金属配合物催化剂将以在洗涤母液中提供所需含量的数量存在于本发明的洗涤剂漂白组合物中。通常在洗涤剂漂白组合物中金属配合物催化剂含量相应于按重量计0.0005%-0.5%的铁、锰或铜含量。当洗涤剂漂白组合物的剂量相对低时,例如约1-2g/l,在配方中金属含量合适地为按重量计0.0025-0.5%,优选0.005-0.25%。在较高产品剂量时,如例如用于欧洲消费者时,配方中的金属含量合适地为按重量计0.0005-0.1%,优选0.001-0.05%。
本发明的洗涤剂漂白组合物在7-13的宽pH范围内是有效的,最佳pH范围为8-11。表面活性物质
本发明的洗涤剂漂白组合物通常以按重量计10-50%的数量含有表面活性物质。表面活性物质可以是天然产生的,例如皂,或合成的物质,其选自阴离子、非离子、两性、两性离子、阳离子活性物质和它们的混合物。许多合适的活性物质是商业上可获得的,并在文献,例如《表面活性剂和洗涤剂》,卷Ⅰ和Ⅱ,Schwartz,Perry and Berch中完整描述。
典型的合成的阴离子表面活性物质通常是带有含约8-约22个碳原子的烷基的有机硫酸盐和磺酸盐的水溶性碱金属盐,所用的术语烷基包括高级芳基的烷基部分。合适的合成阴离子洗涤剂化合物的实例是烷基硫酸钠和铵,尤其是通过硫酸化例如由牛油或椰子油产生的高级(C8-C18)醇所得到的物质;烷基(C9-C20)苯磺酸钠和铵,尤其是直链仲烷基(C10-C15)苯磺酸钠;烷基甘油基醚硫酸钠,尤其是那些由牛油或椰子油脂肪酸单甘油酯硫酸盐和磺酸盐得到的高级醇的醚;高级(C9-C18)脂肪醇烯化氧,尤其是环氧乙烷反应产物的硫酸酯的钠和铵盐;脂肪酸,例如椰子脂肪酸用羟乙磺酸酯化和用氢氧化钠中和的反应产物;甲基牛磺酸的脂肪酸酰胺的钠和铵盐;烷烃单磺酸盐,例如通过使α-烯烃(C8-C20)与亚硫酸氢钠反应得到的物质和通过链烷烃与SO2和Cl2反应,随后用碱水解产生无规磺酸盐得到的物质;(C7-C12)二烷基磺基琥珀酸钠和铵;和烯烃磺酸盐,该术语用于描述通过使烯烃,尤其是(C10-C20)α-烯烃与SO3反应,随后中和和水解反应产物制备的物质。优选的阴离子洗涤剂化合物是(C10-C15)烷基苯磺酸钠和(C16-C18)烷基醚硫酸钠。
可以使用的,优选与阴离子表面活性化合物一起使用的合适非离子表面活性化合物的实例尤其包括烯化氧,通常是环氧乙烷与烷基(C6-C22)苯酚的反应产物,通常是5-25EO,即每分子5-25单元的环氧乙烷;和脂族(C8-C18)伯或仲直链或支链醇与环氧乙烷的缩合产物,通常为2-30EO。其它所谓的非离子表面活性物质包括烷基聚葡糖苷、蔗糖酯、长链叔胺氧化物、长链叔膦氧化物和二烷基亚砜。
两性或两性离子表面活性化合物也可用于本发明的组合物中,但由于其相对高的成本,不是通常需要的。如果使用两性或两性离子洗涤剂化合物,基于更常用的合成阴离子和非离子活性物质,它通常以少量存在于组合物中。
本发明的洗涤剂漂白组合物优选含有按重量计1-15%阴离子表面活性剂和按重量计10-40%非离子表面活性剂,在进一步优选的实施方案中,洗涤剂活性物质体系不含C16-C12脂肪酸皂。洗涤助洗剂
本发明的洗涤剂漂白组合物通常并优选还含有按重量计约5-80%,优选按重量计约10-60%的洗涤助洗剂。
助洗剂物质可选自1)钙螯合物质,2)沉淀物质,3)钙离子交换物质和4)它们的混合物。
钙螯合剂助洗剂物质的实例包括碱金属聚磷酸盐,例如是三聚磷酸钠、次氮基三乙酸和其水溶性盐;羧基甲基氧基琥珀酸、乙二胺四乙酸、氧联二琥珀酸、苯六酸、苯多羧酸、柠檬酸的碱金属盐和在US-A-4144226和US-A-4146495中描述的聚缩醛羧酸盐。
沉淀助洗剂的实例包括正磷酸钠和碳酸钠。
钙离子交换助洗剂物质的实例包括各种类型的水不溶性结晶或无定形硅铝酸盐,其中,沸石是最知名的代表,例如沸石A、沸石B(也称为沸石P)、沸石C、沸石X、沸石Y和如EP-A-0384070中所述的沸石P型。
本发明的组合物尤其可含有任何一种有机和无机助洗剂物质,虽然,由于环境原因,磷酸盐助洗剂优选被省去或仅以非常小的量使用。用于本发明的典型助洗剂是例如碳酸钠、方解石/碳酸盐、次氮基三乙酸的钠盐、柠檬酸钠、羧基甲氧基丙二酸盐、羧基甲氧基琥珀酸盐和水不溶性结晶或无定形硅铝酸盐助洗剂物质,每种可以单独或与少量作为辅助助洗剂的其它助洗剂或聚合物的混合物用作主助洗剂。
如果组合物的pH位于至多10的较低碱性区域,组合物优选含有不超过按重量计5%的碳酸盐助洗剂,表示为碳酸钠,更优选不超过按重量计2.5%至基本上没有。其它组分
除了上述所提到的组分之外,本发明的洗涤剂漂白组合物可以以通常用于织物洗涤洗涤剂组合物中的数量含有任何常规添加剂。这些添加剂的实例包括缓冲剂,例如碳酸盐、泡沫促进剂,例如链烷醇酰胺,尤其是由棕榈仁脂肪酸和椰子脂肪酸得到的单乙醇酰胺;抑泡剂,例如烷基磷酸盐和聚硅氧烷;抗再沉积剂,例如羧基甲基纤维素钠和烷基或取代烷基纤维素醚;稳定剂,例如膦酸衍生物(例如Dequest型);织物柔软剂;无机盐和碱性缓冲剂,例如硫酸钠和硅酸钠;和通常非常少量的荧光剂、香料、酶,例如蛋白酶、纤维素酶、脂酶、淀粉酶和氧化酶;杀菌剂和着色剂。
当使用过氧化氢源,例如过硼酸钠或过碳酸钠作为漂白化合物时,如果组合物的pH位于至多10的较低碱性区域,组合物优选含有不超过按重量计5%的碳酸盐缓冲剂,表示为碳酸钠,更优选不超过按重量计2.5%至基本上没有。
在添加剂中,过渡金属螯合剂,例如EDTA和膦酸衍生物,例如EDTMP(乙二胺四(亚甲基膦酸盐))是尤其重要的,因为它们不仅改善了催化剂/H2O2体系和敏感组分,例如酶、荧光剂、香料等的稳定性,还改善了漂白性能,尤其是在超过10的较高pH范围,尤其是在pH10.5和以上时。
本发明将通过如下非限制性实施例进一步说明:
实施例合成:
所有反应在氮气气氛下进行,除非另有说明。所有试剂和溶剂由Aldrich或Across得到,按来样使用,除非另有说明。石油醚40-60在作洗脱剂使用前用旋转蒸发器蒸馏。快速色谱法用Merck硅胶60或氧化铝90(根据Brockmann活性Ⅱ-Ⅲ)进行。1H NMR(300MHz)和13C NMR(75MHz)在CDCl3中记录,除非另有说明。多重峰用正常缩写记录,用p表示五重峰。用于配位体合成的起始物料的合成:N-苄基氨基乙腈的合成。将N-苄基胺(5.35g,50mmol)溶解在水∶甲醇混合物(50ml,1∶4)中,加入盐酸(含水,30%)直至pH达到7.0。加入氰化钠(2.45g,50mmol),在冷却到0℃后,加入福尔马林(含水,35%,4.0g,50mmol)。反应用TLC(氧化铝;乙酸乙酯∶乙胺=9∶1)跟踪直至可检测到苄胺。随后真空蒸发甲醇,残余油“溶解”在水中。水相用二氯甲烷(3×50ml)提取,收集有机层,真空除去溶剂。残余物用Kugelrohr蒸馏(p=20mmHg,T=120℃)纯化得到N-苄基氨基乙腈(4.39g,30mmol,60%)无色油状物。
1H NMR:δ7.37-7.30(m,5H),3.94(s,2H),3.57(s,2H),1.67(br s,1H);
13C NMR:δ137.74,128.58,128.46,128.37,127.98,127.62,117.60,52.24,36.19.N-乙基氨基乙腈的合成。合成方法以类似于用于N-苄基氨基乙腈的合成方法进行。然而,检测通过将TLC板浸在高锰酸钾溶液中和加热板直至显示明亮斑点进行。由乙胺(2.25g,50mmol)开始,得到纯N-乙基氨基乙腈(0.68g,8.1mmol,16%)浅黄色油状物。
1H NMR:δ3.60(s,2H),2.78(q,J=7.1,2H),1.22(br s,1H),1.14(t,J=7.2,3H);
13C NMR:δ117.78,43.08,37.01,14.53.N-乙基乙-1,2-二胺的合成。合成方法由N-乙基氨基乙腈开始根据Hageman;J.Org.Chem,;14;1949;616,634进行。N-苄基乙-1,2-二胺的合成。将氢氧化钠(890mg,22.4mmol)溶解在乙醇(96%,20ml)中,该过程花费2小时。加入N-苄基氨基乙腈(4,2.92g,20mmol)和雷内镍(约0.5g),施加氢压(p=3.0atm)直至氢气吸收停止。混合物通过Gellite过滤,用乙醇洗涤残余物。过滤器不应在干燥的情况下操作,因为雷内镍是相对引火的。含有雷内镍的Cellite通过将混合物放置在稀酸中破坏,导致气体产生。真空蒸发乙醇,残余物溶解在水中。加入碱后(含水氢氧化钠,5N),油化出产物,用氯仿提取(3×20ml)。在真空蒸发溶剂后,1H NMR显示存在苄胺。用柱色谱法(硅胶;甲醇∶乙酸乙酯∶三乙胺=1∶8∶1)进行分离产生苄胺,随后用溶剂混合物甲醇∶乙酸乙酯∶三乙胺=5∶4∶1。在TLC中用氧化铝作为固相进行检测,得到纯N-苄基乙-1,2-二胺(2.04g,13.6mmol,69%)。
1H NMR:δ7.33-7.24(m,5H),3.80(s,2H),2.82(t,J=5.7,2H),2.69(t,J=5.7,
2H),1.46(br s,3H);
13C NMR:δ140.37,128.22,127.93,126.73,53.73,51.88,41.66.2-乙酰氧基甲基-5-甲基吡啶的合成。将2,5-二甲基吡啶(31.0g,290mmol)、乙酸(180ml)和过氧化氢(30ml,30%)在70-80℃下加热3小时。加入过氧化氢(24ml,30%),随后混合物在60-70℃下加热16小时。真空(旋转蒸发,水浴50℃,直至p=20mbar)除去大多数(大概)过氧化氢、水、乙酸和过乙酸的混合物。在回流加热下将得到的含有N-氧化物的混合物滴加到乙酐中。该反应是高放热的,通过滴加速度控制。在回流加热1小时后,滴加甲醇。该反应是高放热的,得到的混合物再回流加热30分钟。在蒸发甲醇(旋转蒸发,50℃,直至p=20mbar)后,得到的混合物用Kugelrohr蒸馏(p=20mmHg,T=150℃)纯化。得到的透明油状物仍含有乙酸,这通过提取(二氯甲烷,碳酸氢钠(饱和))除去得到纯2-乙酰氧基甲基-5-甲基吡啶乙酯(34.35g,208mmol,72%),为浅黄色油状物。
1H NMR:δ8.43(s,1H),7.52(dd,J=7.8,J=1.7,1H),7.26(d,J=7.2,1H),5.18(s,
2H),2.34(s,3H),2.15(s,3H);
13C NMR:δ170.09,152.32,149.39,136.74,131.98,121.14,66.31,20.39,17.66.2-乙酰氧基甲基-5-乙基吡啶的合成。该合成方法以类似于2-乙酰氧基甲基-5-甲基吡啶的合成方法进行。由5-乙基-2-甲基吡啶(35.10g,290mmol)开始,得到纯2-乙酰氧基甲基-5-乙基吡啶(46.19g,258mmol,89%)浅黄色油状物。
1H NMR:δ8.47(s,1H),7.55(d,J=7.8,1H),7.29(d,J=8.1,1H),2.67(q,J=7.8,
2H),2.14(s,3H),1.26(t,J=7.77,3H);
13C NMR:δ170.56,152.80,149.11,138.47,135.89,121.67,66.72,25.65,20.78,
15.13.2-乙酰氧基甲基-3-甲基吡啶的合成。该合成方法以类似于2-乙酰氧基甲基-5-甲基吡啶的合成方法进行。唯有的差异是颠倒Kugelrohr蒸馏和提取。根据1H NMR,得到乙酸酯和相应醇的混合物。由2,3-二甲基吡啶(31.0g,290mmol)开始,得到纯2-乙酰氧基甲基-3-甲基吡啶(46.19g,258mmol,89%,用纯乙酸酯计算)浅黄色油状物。
1H NMR:δ8.45(d,J=3.9,1H),7.50(d,J=8.4,1H),7.17(dd,J=7.8,J=4.8,1H),
5.24(s,2H),2.37(s,3H),2.14(s,3H).2-羟基甲基-5-甲基吡啶的合成。将2-乙酰氧基甲基-5-甲基吡啶(30g,182mmol)溶解在盐酸(100ml,4N)中,将混合物回流加热直至TLC(硅胶;三乙胺∶乙酸乙酯∶石油醚40-60=1∶9∶19)显示完全不存在乙酸酯(通常1小时)。冷却混合物,转化为pH>11,用二氯甲烷(3×50ml)提取,真空除去溶剂。通过Kugelrohr蒸馏(p=20mmHg,T=130℃)得到纯2-羟基甲基-5-甲基吡啶(18.80g,152mmol,84%)浅黄色油状物。
1H NMR:δ8.39(s,1H),7.50(dd,J=7.8,J=1.8,1H),7.15(d,J=8.1,1H),4.73
(s,2H),3.83(br s,1H),2.34(s,3H);
13C NMR:δ156.67,148.66,137.32,131.62,120.24,64.12,17.98.2-羟基甲基-5-乙基吡啶的合成。该合成方法以类似于用于2-羟基甲基-5-甲基吡啶的合成方法进行,由2-乙酰氧基甲基-5-乙基吡啶(40g,223mmol)开始,得到纯2-羟基甲基-5-乙基吡啶(26.02g,189mmol,85%)浅黄色油状物。
1H NMR:δ8.40(d,J=1.2,1H),7.52(dd,J=8.0,J=2.0,1H),7.18(d,J=8.1,
1H),4.74(s,2H),3.93(br s,1H),2.66(q,J=7.6,2H),1.26(t,J=7.5,3H);
13C NMR:δ156.67,148.00,137.87,136.13,120.27,64.07,25.67,15.28.2-羟基甲基-3-甲基吡啶的合成。该合成方法以类似于用于2-羟基甲基-5-甲基吡啶的合成方法进行,由2-乙酰氧基甲基-3-甲基吡啶(25g,(对混合物重新计算),152mmol)开始,得到纯2-羟基甲基-3-甲基吡啶(15.51g,126mmol,83%)浅黄色油状物。
1H NMR:δ8.40(d,J=4.5,1H)),7.47(d,J=7.2,1H),7.15(dd,J=7.5,J=5.1,
1H),4.85(br s,1H),4.69(s,1H),2.22(s,3H);
13C NMR:δ156.06,144.97,137.38,129.53,121.91,61.38,16.30.配位体合成:N-甲基-N,N’,N’-三(吡啶-2-基甲基)乙-1,2-二胺(L1)的合成。配位体L1(比较)根据Bernal,Ivan;Jensen,Inge Margrethe;Jensen,Kenneth B.;McKenzie,Christine J.;Toftlund,Hans;Tuchagues,Jean-Pierre;J.Chem.Soc.Dalton Trans.;22,1995;3667-3676所述制备。N-甲基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L2,Me-TRILEN)的合成。将2-羟基甲基-3-甲基吡啶(5.00g,40.7mmol)溶解在二氯甲烷(30ml)中,在冷却(冰浴)下滴加亚硫酰氯(30ml)。将得到的混合物搅拌1小时,真空除去溶剂(旋转蒸发,直至p=20mmHg,T=50℃)。向得到的混合物中加入二氯甲烷(25ml),随后滴加氢氧化钠(5N,含水)直至pH(水)≥11。在开始时反应相当剧烈,因为仍存在部分亚硫酰氯。加入N-甲基乙-1,2-二胺(502mg,6.8mmol)和附加的氢氧化钠(5N,10ml),反应混合物在室温下搅拌45小时。将混合物倾入水(200ml)中,检查pH(≥14,否则加入氢氧化钠(含水5N))。反应混合物用二氯甲烷提取(3或4×50ml,直至用TLC检测不到产物)。将合并的有机相干燥,真空除去溶剂。如上所述进行纯化得到N-甲基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺浅黄色油状物。用柱色谱法(氧化铝90(根据Brockmann活性Ⅱ-Ⅲ);三乙胺∶乙酸乙酯∶石油醚40-60=1∶9∶10)进行纯化直至根据TLC(氧化铝,相同的洗脱剂,Rf≈0.9)除去杂质。化合物用乙酸乙酯∶三乙胺=9∶1洗脱,得到N-甲基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L2,1.743g,4.30mmol,63%)。
1H NMR:δ8.36(d,J=3.0,3H),7.40-7.37(m,3H),7.11-7.06(m,3H),3.76(s,
4H),3.48(s,2H),2.76-2.71(m,2H),2.53-2.48(m,2H),2.30(s,3H),2.12(s,6H),2.05
(s,3H);
13C NMR:δ156.82,156.77,145.83,145.67,137.61,133.14,132.72,122.10,121.88,
62.32,59.73,55.19,51.87,42.37,18.22,17.80.N-乙基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L3,Et-TRILEN)的合成。该合成方法以类似于L2的合成方法进行。由2-羟基甲基-3-甲基吡啶(25.00g,203mmol)和N-乙基乙-1,2-二胺(2.99g,34.0mmol),得到N-乙基-N,N’,N’-三(甲基吡啶-2-基甲基)乙-1,2-二胺(L3,11.49g,28.5mmol,84%)。柱色谱法(氧化铝;三乙胺∶乙酸乙酯∶石油醚40-60=1∶9∶30,随后三乙胺∶乙酸乙酯=1∶9)。
1H NMR: δ8.34-8.30(m,3H),7.40-7.34(m,3H),7.09-7.03(m,3H),3.71(s,
4H),3.58(s,2H),2.64-2.59(m,2H),2.52-2.47(m,2H),2.43-2.36(m,2H),2.31(s,
3H),2.10(s,6H),0.87(t,J=7.2,3H);
13C NMR:δ157.35,156.92,145.65,137.61,133.14,132.97,122.09,121.85,59.81,
59.28,51.98,50.75,48.02,18.27,17.80,11.36.N-苄基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L4,Bn-TRILEN)的合成。该合成方法以类似于L2的合成方法进行。由2-羟基甲基-3-甲基吡啶(3.00g,24.4mmol)和N-苄基乙-1,2-二胺(610mg,4.07mmol),得到N-苄基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L4,1.363g,2.93mmol,72%)。柱色谱法(氧化铝;三乙胺∶乙酸乙酯∶石油醚40-60=1∶9∶10)。
1H NMR:δ8.33-8.29(m,3H),7.37-7.33(m,3H),7.21-7.03(m,8H),3.66(s,
4H),3.60(s,2H),3.42(s,2H),2.72-2.67(m,2H),2 50-2.45(m,2H),2.23(s,3H),2.03
(s,6H);
13C NMR:δ157.17,156.96,145.83,145.78,139.29,137.91,137.80,133.45,133.30,
128.98,127.85,126.62,122.28,122.22,59.99,58.83,51.92,51.54,18.40,17.95.N-羟基乙基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L5)的合成。该合成方法以类似于L6的合成方法进行。由2-羟基甲基-3-甲基吡啶(3.49g,28.4mmol)和N-羟基乙基乙-1,2-二胺(656mg,6.30mmol),7天后得到N-羟基乙基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L5,379mg,0.97mmol,14%)。
1H NMR:δ8.31-8.28(m,3H),7.35-7.33(m,3H),7.06-7.00(m,3H),4.71(br s,
1H),3.73(s,4H),3.61(s,2H),3.44(t,J=5.1,2H),2.68(s,4H),2.57(t,J=5.0,2H),
2.19(s,3H),2.10(s,6H);
13C NMR:δ157.01,156.88,145.91,145.80,137.90,137.83,133.30,131.89,122.30,
121.97,59.60,59.39,57.95,56.67,51.95,51.22,18.14,17.95.N-甲基-N,N’,N’-三(5-甲基吡啶-2-基甲基)乙-1,2-二胺(L6)的合成。将2-羟基甲基-5-甲基吡啶(2.70g,21.9mmol)溶解在二氯甲烷(25ml)中,在冷却(冰浴)下滴加亚硫酰氯(25ml)。将得到的混合物搅拌1小时,真空除去溶剂(旋转蒸发,直至p=20mmHg,T±35℃)。残余的油状物直接用于配位体的合成,因为由文献已知,游离吡啶甲基氯有些不稳定,是十分催泪的。向得到的混合物中加入二氯甲烷(25ml)和N-甲基乙-1,2-二胺(360mg,4.86mmol),随后滴加氢氧化钠(5N,含水)。在开始时反应相当剧烈,因为仍存在部分亚硫酰氯。水层调节到pH=10,加入附加的氢氧化钠(5N,4.38ml)。搅拌反应混合物直至样品显示完全转化(7天)。反应混合物用二氯甲烷提取(3×25ml)。将合并的有机相干燥,真空除去溶剂。用柱色谱法(氧化铝90(根据Brockmann活性Ⅱ-Ⅲ);三乙胺∶乙酸乙酯∶石油醚40-60=1∶9∶10)进行纯化直至根据TLC(氧化铝,相同的洗脱剂,Rf≈0.9)除去杂质。化合物用乙酸乙酯∶三乙胺=9∶1洗脱,得到N-甲基-N,N’,N’-三(5-甲基吡啶-2-基甲基)乙-1,2-二胺(L6,685mg,1.76mmol,36%)浅黄色油状物。
1H NMR:δ8.31(s,3H)7.43-7.35(m,5H),7.21(d,J=7.8,1H),3.76(s,4H),3.56
(s,2H),2.74-2.69(m,2H),2.63-2.58(m,2H),2.27(s,6H),2.16(s,3H);
13C NMR;δ156.83,156.43,149.23,149.18,136.85,136.81,131.02,122.41,122.30,
63.83,60.38,55.53,52.00,42.76,18.03.N-甲基-N,N’,N’-三(5-乙基吡啶-2-基甲基)乙-1,2-二胺(L7)的合成。该合成方法以类似于L6的合成方法进行。由2-羟基甲基-5-乙基吡啶(3.00g,21.9mmol)和N-甲基乙-1,2-二胺(360mg,4.86mmol),7天后得到N-甲基-N,N’,N’-三(5-乙基吡啶-2-基甲基)乙-1,2-二胺(L7,545mg,1.26mmol,26%)。
1H NMR:δ8.34(s,3H),7.44-7.39(m,5H),7.26(d,J=6.6,1H),3.80(s,4H),3.59
(s,2H),2.77-2.72(m,2H),2.66-2.57(m,8H),2.18(s,3H),1.23(t,J=7.5,9H);
13C NMR:δ157.14,156.70,148.60,148.53,137.25,135.70,122.59,122.43,63.91,
60.48,55.65,52.11,42.82,25.73,15.36.金属-配位体配合物的合成:N-甲基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺氯化铁(Ⅱ).PF6([L2Fe(Ⅱ)Cl]PF6)的合成。将FeCl2.4H2O(51.2mg,257μmol)溶解在甲醇∶水=1∶1(2.5ml)中,溶液加热到50℃,加入在甲醇∶水=1∶1(2.0ml)中的N-甲基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L2,100mg,257μmol),随后滴加在水(2.5ml)中的NaPF6(86.4mg,514μmol)。冷却到室温,过滤和真空干燥(p=0.05mmHg,T=室温)得到配合物[L2Fe(Ⅱ)Cl]PF6(149mg,239μmol,93%)黄色固体。
1H NMR(CD3CN,顺磁):δ167.17,142.18,117.01,113.34,104.79,98.62,
70.77,67.04,66.63,58.86,57.56,54.49,51.68,48.56,45.90,27.99,27.36,22.89,20.57,
14.79,12.14,8.41,8.16,7.18,6.32,5.78,5.07,4.29,3.82,3.43,2.91,2.05,1.75,1.58,
0.94,0.53,-0.28,-1.25,-4.82,-18.97,-23.46.N-乙基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺氯化铁(Ⅱ).PF6([L3Fe(Ⅱ)Cl]PF6)的合成。该合成方法类似于[L2Fe(Ⅱ)Cl]PF6的合成方法进行。由N-乙基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L3,104mg,257μmol)开始,得到配合物[L3Fe(Ⅱ)Cl]PF6(146mg,229μmol,89%)黄色固体。
1H NMR(CD3CN,顺磁):δ165.61,147.20,119.23,112.67,92.92,63.14,
57.44,53.20,50.43,47.80,28.59,27.09,22.48,8.55,7.40,3.63,2.95,2.75,2.56,2.26,
1.75,1.58,0.92,0.74,-0.28,-1.68,-2.68,-12.36,-28.75.N-苄基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺氯化铁(Ⅱ).PF6([L4Fe(Ⅱ)Cl]PF6)的合成。该合成方法类似于[L2Fe(Ⅱ)Cl]PF6的合成方法进行。由N-苄基-N,N’,N’-三(3-甲基吡啶-2-基甲基)乙-1,2-二胺(L4,119.5mg,257μmol)开始,得到配合物(172mg,229μmol,95%)黄色固体。
1H NMR(CD3CN,顺磁):δ166.33,145.09,119.80,109.45,92.94,57.59,
52.83,47.31,28.40,27.89,16.28,11.05,8.70,8.45,7.69,6.99,6.01,4.12,2.89,2.71,
1.93,1.56,-0.28,-1.68,-2.58,-11.40,-25.32.实验:
实验在配备磁搅拌器、热电偶和pH电极的温度控制烧杯中进行,漂白实验在40和60℃下进行。在实施例中,当使用配方时,剂量为约5g/l总配方。没有漂白剂的基础配方组合物描述如下:洗涤剂配方阴离子表面活性剂: 9%非离子表面活性剂: 7%皂: 1%沸石: 30%聚合物: 3%碳酸钠: 7%酶颗粒: 1%硅酸钠: 5%柠檬酸钠: 3.5%Dequest2047: 1%过碳酸盐: 19%TAED颗粒(83%) 5.5%水和微量组分: 8%
总共使用8.6mmol/l H2O2,以过碳酸钠形式调配剂量。pH调节到10.0,漂白过程进行30分钟。
茶渍试验布(BC-1)用作漂白监测物。在漂白实验后,布在自来水中漂洗,在滚筒干燥器中干燥。在洗涤之前和之后用MinoltaCM3700d分光光度计测量反射度(R460*),取2个试验布的平均值,用ΔR值表示的反射度的差值在如下表格中给出。
实施例1
配位体/金属盐混合物以浓度10μmol/l高氯酸铁和50μmol/l配位体调配剂量,这些混合物通过将铁盐和配位体溶解在乙醇中制备,将10ml该备料溶液加入漂白溶液中。
ΔR:H2O2(无缓冲液) 7.4点高氯酸铁+L1: 13.7点高氯酸铁+L2: 16.8点高氯酸铁+L3: 16.3点高氯酸铁+L4: 14.3点高氯酸铁+L5: 14.0点高氯酸铁+L6: 13.2点高氯酸铁+L7: 13.5点
这些结果显示相对于对照组这些配合物的明显效果。与环未取代的配位体L1(“Trispicen”)相比,使用环取代的配位体L2-L5,尤其是L2(“Me-Trilen”)和L3(“Et-Trilen”)的混合物显示效果。
实施例2
明确定义的金属-配位体配合物与实施例1所述相同调配剂量,只是在40℃下使用10μM催化剂,8.8mmol/lH2O2,无缓冲剂,pH10.0:
ΔR:-无催化剂: 6.5点-[Fe(L2)Cl]PF6: 15.7点-[Fe(L3)Cl]PF6: 14.8点-[Fe(L4)Cl]PF6: 12.7点
实施例3
在40℃下明确定义的金属-配位体配合物与实施例2所述相同调配剂量,只是使用5μM催化剂,在10mmol/l碳酸盐缓冲液中的8.8mmol/lH2O2,pH10.0:
ΔR:-无催化剂: 7.4点-[Fe(L2)Cl]PF6: 15.9点-[Fe(L3)Cl]PF6: 14.4点-[Fe(L4)Cl]PF6: 11.3点
实施例4
在40℃下明确定义的金属-配位体配合物与实施例3所述相同调配剂量,只是存在5g/L没有TAED的洗涤剂配方(8.8mmol/lH2O2,pH10.0):
ΔR:-无催化剂: 8.6点-[Fe(L2)Cl]PF6: 14.9点-[Fe(L3)Cl]PF6: 14.4点-[Fe(L4)Cl]PF6: 11.1点
实施例5
明确定义的金属-配位体配合物与实施例3所述相同调配剂量,只是存在5g/L含有TAED的洗涤剂配方(得到8.7mmol/lH2O2和2mmol/l过乙酸):
ΔR:-无催化剂: 11.3点-[Fe(L2)Cl]PF6: 19.6点-[Fe(L3)Cl]PF6: 17.4点
实施例6
明确定义的金属-配位体配合物与实施例3所述相同调配剂量,只是在60℃:
ΔR:-无催化剂: 12.7点-[Fe(L2)Cl]PF6: 21.6点-[Fe(L3)Cl]PF6: 19.1点-[Fe(L4)Cl]PF6: 15.3点
实施例7
在60℃下明确定义的金属-配位体配合物与实施例6所述相同调配剂量,只是存在5g/L没有TAED的洗涤剂配方:
ΔR:-无催化剂: 14.2点-[Fe(L2)Cl]PF6: 20.5点-[Fe(L3)Cl]PF6: 18.8点-[Fe(L4)Cl]PF6: 16.5点
这些结果显示类似于铁盐/配位体混合物,明确定义的铁-配位体配合物提供高漂白活性。活性排列为Me-Trilen>Et-Trilen>Bz-Trilen。配合物催化剂在含有或没有TAED的洗涤剂配方中也是活性的。还有,在不存在或存在配方的情况下,配合物催化剂在60℃下都是活性的。
Claims (17)
1.含有通式(A)配合物的漂白和氧化催化剂:
[LMXn]zYq (A)其中
M表示Ⅱ、Ⅲ、Ⅳ或Ⅴ氧化态的铁,Ⅱ、Ⅲ、Ⅳ、Ⅵ或Ⅶ氧化态的锰或Ⅰ、Ⅱ或Ⅲ氧化态的铜;
X表示配位物质;
n表示零或0-3的整数;
z表示配合物的电荷,是整数,它可以是正数、零或负数;
Y表示抗衡离子,其类型取决于配合物的电荷;
q=z/[电荷Y];
L表示通式(B)的五齿配位体:
R1R1N-W-NR1R2 (B)其中每个R1分别表示-R3-V,其中R3表示选择性地取代的亚烷基、亚烯基、氧基亚烷基、氨基亚烷基或亚烷基醚,和V表示取代的选自吡啶基、吡嗪基、吡唑基、咪唑基、苯并咪唑基、嘧啶基、三唑基和噻唑基的杂芳基;
W表示选择性地取代的亚烷基桥基,其选自-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-和-CH2-C6H4-CH2-;
R2表示选自烷基和芳基的基团,它选择性地被选自羟基、烷氧基、羧酸盐、羧酰胺、羧酸酯、磺酸盐、胺、烷基胺和N+(R4)3的取代基取代,其中R4选自H、烷基、烯基、芳烷基、芳烯基、氧基烷基、氧基烯基、氨基烷基、氨基烯基、烷基醚和烯基醚。
2.权利要求1的催化剂,其中M是Ⅱ、Ⅲ、Ⅳ或Ⅴ氧化态的铁。
3.权利要求1或2的催化剂,其中W表示亚乙基。
4.任一上述权利要求的催化剂,其中V表示取代的吡啶-2-基。
5.任一上述权利要求的催化剂,其中R3表示亚甲基,V表示甲基取代或乙基取代的吡啶-2-基。
6.任一上述权利要求的催化剂,其中V表示3-甲基吡啶-2-基。
7.任一上述权利要求的催化剂,其中R2表示选自甲基、乙基、苄基、2-羟基乙基和2-甲氧基乙基的基团。
8.权利要求7的催化剂,其中R2表示选自甲基和乙基的基团。
9.任一上述权利要求的催化剂,其中配位体L是N-甲基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺或N-乙基-N,N’,N’-三(3-甲基-吡啶-2-基甲基)乙-1,2-二胺。
10.任一上述权利要求的催化剂,其中X是选自CH3CN、H2O、F-、Cl-、Br-、OOH-、O2 2-、O2 -、R5COO-、R5O-、LMO-和LMOO-的配位剂,其中R5表示H或选择性地取代的苯基、萘基或C1-C4烷基。
11.任一上述权利要求的催化剂,其中抗衡离子Y选自R6COO-、ClO4 -、BF4 -、PF6 -、R6SO3 -、R6SO4 -、SO4 2-、NO3 -、F-、Cl-、Br-和I-,其中R6表示H或选择性地取代的苯基、萘基或C1-C4烷基。
12.含有配位体L或产生配位体L的物质和金属M盐的组合物,其中就地形成如任一上述权利要求中定义的催化剂。
13.含有过氧漂白化合物和任一上述权利要求中定义的催化剂的组合物。
14.权利要求13的组合物,其含有按重量计2-35%的过氧漂白化合物和相当于按重量计0.0005-0.5%的金属含量的催化剂。
15.权利要求13或14的组合物,其中过氧漂白化合物选自过氧化氢、释放或产生过氧化氢的化合物、过氧酸和它们的盐,和它们的混合物,选择性地和过氧酸漂白前体一起。
16.权利要求13-15之一的组合物,其还含有表面活性物质和洗涤助洗剂。
17.权利要求16的组合物,含有按重量计10-50%的表面活性物质和按重量计5-80%的洗涤助洗剂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98309169.5 | 1998-11-10 | ||
EP98309169A EP1001009B1 (en) | 1998-11-10 | 1998-11-10 | Bleach and oxidation catalyst |
Publications (2)
Publication Number | Publication Date |
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CN1325436A true CN1325436A (zh) | 2001-12-05 |
CN1227347C CN1227347C (zh) | 2005-11-16 |
Family
ID=8235154
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB998130893A Expired - Fee Related CN1227347C (zh) | 1998-11-10 | 1999-10-25 | 漂白和氧化催化剂 |
Country Status (12)
Country | Link |
---|---|
US (1) | US6140294A (zh) |
EP (2) | EP1001009B1 (zh) |
CN (1) | CN1227347C (zh) |
AR (1) | AR021117A1 (zh) |
AU (1) | AU749674B2 (zh) |
BR (1) | BR9915193B1 (zh) |
CA (1) | CA2350571C (zh) |
DE (1) | DE69817832T2 (zh) |
ES (1) | ES2206853T3 (zh) |
TR (1) | TR200101313T2 (zh) |
WO (1) | WO2000027976A1 (zh) |
ZA (1) | ZA200103295B (zh) |
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Publication number | Priority date | Publication date | Assignee | Title |
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Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69125309T2 (de) * | 1990-05-21 | 1997-07-03 | Unilever Nv | Bleichmittelaktivierung |
FR2692499B1 (fr) * | 1992-06-22 | 1994-08-26 | Atochem Elf Sa | Procédé de délignification et de blanchiment d'une matière lignocellulosique. |
EP0765381B1 (en) * | 1994-06-13 | 1999-08-11 | Unilever N.V. | Bleach activation |
FR2741340B1 (fr) * | 1995-11-16 | 1997-12-26 | Elf Aquitaine | Procede d'oxydation de substrats organiques en presence de complexes metalliques de ligands tetra-, penta- et hexacoordinants et catalyseurs d'oxydation les contenant |
DE19605688A1 (de) * | 1996-02-16 | 1997-08-21 | Henkel Kgaa | Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen |
EP0906402A1 (en) * | 1996-06-19 | 1999-04-07 | Unilever N.V. | Bleach activation |
DE19713851B4 (de) * | 1997-04-04 | 2006-07-20 | Henkel Kgaa | Verwendung von Komplexen des Molybdäns, Vanadiums oder Wolframs zur Verstärkung der Bleichwirkung |
CA2248476A1 (en) * | 1997-10-01 | 1999-04-01 | Unilever Plc | Bleach activation |
-
1998
- 1998-11-10 DE DE69817832T patent/DE69817832T2/de not_active Expired - Lifetime
- 1998-11-10 ES ES98309169T patent/ES2206853T3/es not_active Expired - Lifetime
- 1998-11-10 EP EP98309169A patent/EP1001009B1/en not_active Expired - Lifetime
-
1999
- 1999-10-25 CN CNB998130893A patent/CN1227347C/zh not_active Expired - Fee Related
- 1999-10-25 AU AU12682/00A patent/AU749674B2/en not_active Ceased
- 1999-10-25 EP EP99955934A patent/EP1129170A1/en not_active Withdrawn
- 1999-10-25 BR BRPI9915193-6A patent/BR9915193B1/pt not_active IP Right Cessation
- 1999-10-25 CA CA002350571A patent/CA2350571C/en not_active Expired - Fee Related
- 1999-10-25 TR TR2001/01313T patent/TR200101313T2/xx unknown
- 1999-10-25 WO PCT/EP1999/008325 patent/WO2000027976A1/en not_active Application Discontinuation
- 1999-11-03 US US09/433,157 patent/US6140294A/en not_active Expired - Lifetime
- 1999-11-08 AR ARP990105642A patent/AR021117A1/es active IP Right Grant
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2001
- 2001-04-23 ZA ZA2001/03295A patent/ZA200103295B/en unknown
Cited By (6)
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CN103174007A (zh) * | 2011-11-24 | 2013-06-26 | 东华大学 | 三吡啶基四氮金属配合物在纺织品低温练漂助剂中的应用 |
CN103174009A (zh) * | 2011-11-24 | 2013-06-26 | 东华大学 | 三吡啶基五氮金属配合物在纺织品低温练漂助剂中的应用 |
CN103174007B (zh) * | 2011-11-24 | 2015-05-13 | 东华大学 | 三吡啶基四氮金属配合物在纺织品低温练漂助剂中的应用 |
CN105164241A (zh) * | 2013-05-02 | 2015-12-16 | 艺康美国股份有限公司 | 用于在餐具洗涤应用中的改进的淀粉去除的浓缩洗涤剂组合物 |
CN104631085A (zh) * | 2015-02-05 | 2015-05-20 | 南通鑫唐纺织印染有限公司 | 一种竹纤维纱线低温漂白工艺 |
CN104631085B (zh) * | 2015-02-05 | 2017-10-24 | 南通鑫唐纺织印染有限公司 | 一种竹纤维纱线低温漂白工艺 |
Also Published As
Publication number | Publication date |
---|---|
CA2350571C (en) | 2009-01-06 |
DE69817832D1 (de) | 2003-10-09 |
TR200101313T2 (tr) | 2001-10-22 |
CN1227347C (zh) | 2005-11-16 |
ES2206853T3 (es) | 2004-05-16 |
BR9915193B1 (pt) | 2009-01-13 |
AU1268200A (en) | 2000-05-29 |
WO2000027976A1 (en) | 2000-05-18 |
BR9915193A (pt) | 2001-08-14 |
EP1129170A1 (en) | 2001-09-05 |
AU749674B2 (en) | 2002-07-04 |
DE69817832T2 (de) | 2004-10-07 |
ZA200103295B (en) | 2002-06-26 |
US6140294A (en) | 2000-10-31 |
EP1001009A1 (en) | 2000-05-17 |
EP1001009B1 (en) | 2003-09-03 |
CA2350571A1 (en) | 2000-05-18 |
AR021117A1 (es) | 2002-06-12 |
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