CN1078719A - 酰氨基过氧羧酸 - Google Patents
酰氨基过氧羧酸 Download PDFInfo
- Publication number
- CN1078719A CN1078719A CN 93103395 CN93103395A CN1078719A CN 1078719 A CN1078719 A CN 1078719A CN 93103395 CN93103395 CN 93103395 CN 93103395 A CN93103395 A CN 93103395A CN 1078719 A CN1078719 A CN 1078719A
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- CN
- China
- Prior art keywords
- carbon
- carboxyl
- crosses
- acid
- alkylidene group
- Prior art date
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- 239000002253 acid Substances 0.000 title description 26
- 150000007513 acids Chemical class 0.000 title description 6
- 125000003368 amide group Chemical group 0.000 title description 4
- -1 amido peracetic acid compound Chemical class 0.000 claims abstract description 45
- 238000004061 bleaching Methods 0.000 claims abstract description 13
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peroxyacetic acid Substances CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 74
- 150000004965 peroxy acids Chemical class 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 18
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 6
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
- 125000002837 carbocyclic group Chemical group 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 5
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- PWXJULSLLONQHY-UHFFFAOYSA-N phenylcarbamic acid Chemical compound OC(=O)NC1=CC=CC=C1 PWXJULSLLONQHY-UHFFFAOYSA-N 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 238000005406 washing Methods 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 150000002148 esters Chemical class 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000004448 titration Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000003599 detergent Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- LMYSNFBROWBKMB-UHFFFAOYSA-N 4-[2-(dipropylamino)ethyl]benzene-1,2-diol Chemical compound CCCN(CCC)CCC1=CC=C(O)C(O)=C1 LMYSNFBROWBKMB-UHFFFAOYSA-N 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910021538 borax Inorganic materials 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000004328 sodium tetraborate Substances 0.000 description 6
- 235000010339 sodium tetraborate Nutrition 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 5
- 229940044174 4-phenylenediamine Drugs 0.000 description 5
- 150000001263 acyl chlorides Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 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
- 239000012535 impurity Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229940077388 benzenesulfonate Drugs 0.000 description 3
- IRXBNHGNHKNOJI-UHFFFAOYSA-N butanedioyl dichloride Chemical compound ClC(=O)CCC(Cl)=O IRXBNHGNHKNOJI-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000003651 hexanedioyl group Chemical group C(CCCCC(=O)*)(=O)* 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZLIYIUNTGKWSTM-UHFFFAOYSA-N 4-aminobenzoic acid;terephthalic acid Chemical compound NC1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=C(C(O)=O)C=C1 ZLIYIUNTGKWSTM-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 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 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
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
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- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 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 2
- 235000007686 potassium Nutrition 0.000 description 2
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- 230000009466 transformation Effects 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
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- SELBYDWAQZQFQB-UPHRSURJSA-N (z)-4-(carboxymethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)COC(=O)\C=C/C(O)=O SELBYDWAQZQFQB-UPHRSURJSA-N 0.000 description 1
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- OQNZFMZDPKAMHH-UHFFFAOYSA-N 1-methoxyethane-1,1,2-tricarboxylic acid Chemical class COC(C(O)=O)(C(O)=O)CC(O)=O OQNZFMZDPKAMHH-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RPGKFFKUTVJVPY-UHFFFAOYSA-N 2-amino-4-methylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(N)=C1 RPGKFFKUTVJVPY-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
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- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 1
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- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/192—Radicals derived from carboxylic acids from aromatic carboxylic acids
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- 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
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Abstract
本发明提供一种通式如下的酰氨基过氧酸化合
物,通式中各基团的含义可见说明书。该酰氨基过氧
酸化合物可用于漂白底物,如洗好的污染过的衣物。
Description
本发明涉及新酰氨基过氧羧酸和它们作为漂白剂,特别是在洗涤织物中的应用。
有机过氧酸以其优良的漂白活性已经久为人知。例如,Humphreys等人的美国专利4642198描述了许多打算用于含水低pH液体的水不溶有机过氧酸。优选的过氧物质是1,2-二过氧十二双酸(DPDA)。表面活性剂,阴离子和非离子两种均用做为过氧酸颗粒的悬浮剂。当与10%表面活性剂配方时,过酸在贮存条件下具有良好的稳定性。当配方中表面活性剂含量增加到22%,一种典型的重油洗涤剂的含量时,DPDA的半寿命急剧下降。例如,Liberti等人的美国专利4992194报告了DPDA在40℃的寿命在pH为4-4.5的重油洗涤剂中仅为1-2周。
另一种有效的过酸是4,4′-磺酰双过氧苯甲酸(SBPB),它具有优良的贮存稳定性,见Dyroff等人的EP0267175。Madison等人的美国专利4822510演示了在含水液体漂白组合物中,SBPB的稳定性比DPDA增加。
Burns等人的美国专利4634551和Burns的美国专利4686063描述了沿着憎水主链具有极性酰氨部分连接的过氧酸。这些物质由选自硼酸和脲的放热控制剂所稳定。详细描述的是一系列n-酰基氨基过氧酸和烷氨基氧基过氧酸。所有这些报告出来的物质均是单一过羧酸。一份有关的专利EP 349 220(P&G)建议使用一种pH为约3.5-6的磷酸盐缓冲液来改进酰氨基过氧酸的贮存性能。
Hoechst AG的EP 0 349 940描述了一系列亚氨基过氧酸,其中主要的是N-邻苯二甲酰氨基己酸(PAP)。亚氨基过氧羧酸在含水体系中的悬浮液可通过使用烷基苯磺酸钠而实现,见EP 0435 379(Akzo N.V.)所报告。在EP 0347 724(Ausimont)中的有关工艺公开了杂环过酸,如N-酰基哌啶过羧酸。WO-90/14336(Interox)公开了6,6′-对苯二甲-二(酰氨基过氧己)酸和6,6′-富马酰双(酰氨基过氧己)酸。
虽然许多酰氨基和亚氨基过氧酸具有相当显著的漂白活性,但它们在表面活性剂溶液中的稳定性仍有相当大的问题。很清楚,需要为重油洗涤液特别设计新的过酸。这些物质也需要在热和震动敏感性方面和贮存稳定性方面是物理上稳定的。
申请人已经发现,一类过氧羧酸当其悬浮于含水介质中时,具有效的漂白活性和良好的贮存性能。这些过氧羧酸容易地用于全配制的重油洗涤剂组合物中。
因此,本发明提供具有下式的一类酰氨基过氧酸化合物:
其中:
R选自1-12碳亚烷基、5-12碳环亚烷基、6-12碳亚芳基和这些基团的组合;
R1和R2各自选自H、1-16碳烷基、6-12碳芳基和能与R3和二个氮原子形成一个3-12碳环的基;
R3选自1-12碳亚烷基、5-12碳环亚烷基和6-12碳亚芳基,以及倘若R3是亚芳基,n′和m′各为零时,R不是5碳亚烷基;
n和n′各为一整数,其总和为1;
m和m′各为一整数,其总和为1;
M选自H、碱金属、碱土金属、铵、链烷醇铵阳离子和基团及其组合;
在该通式中,有两个亚类结构特别优良。其结构如下:
其中:
R1、R2和R3的定义同上。
代表结构式(Ⅱ)的特别优选的化合物如下:
代表结构式(Ⅲ)的特别优选的化合物如下:
本发明的化合物的合成方法是,将含二功能团的胺和酸缩合生成由二酰氨部分连接的二酸或二酯。使用这种化学原理,已经进行了一系列二胺与对苯二甲酸或己二酸的单酰氯单酯的两个等当物的缩合,以提供一些新的二酰氨二酯。相似地,4-氨基苯甲酸已与二酰氯缩合,生成了二酰氨二酸。
表1列出了一些这种试验的合成。
表1 合成二酰氨二酯的缩合
酸衍生物 胺衍生物
4-羰甲氧基苯甲酰氯 亚乙基二胺
4-羰甲氧基苯甲酰氯 丁二胺
4-羰甲氧基苯甲酰氯 哌嗪
4-羰甲氧基苯甲酰氯 反-1,4-二氨基环己烷
4-羰甲氧基苯甲酰氯 1,4-亚苯基二胺
4-羰甲氧基苯甲酰氯 1,2-亚苯基二胺
羰乙氧基已二酰氯 1,4-亚苯基二胺
羰乙氧基已二酰氯 亚乙基二胺
琥珀酰氯 4-氨基苯甲酸
对苯二酰氯 4-氨基苯甲酸
二胺与酰氯的缩合的实现办法是,在室温下将酰氯的甲苯溶液逐滴加入二胺和过量碳酸钾的水溶液中。生成的肼从二相反应介质中沉淀出来。
对于本发明的目的而言,这里不包括亚氨基结构。
第二种方法可用于那些对水特别敏感的体系。当胺和酰氯均溶于氯仿时,可进行无水制备。吡啶或三乙胺可用作为除去氯化氢的碱。该步骤特别适用于如SDPCA和1,2-PCBPD等化合物。对于许多酰胺,可有一种以上方法用于成功地制备它们。二酰氨二酯或二酸转化为二过氧酸可使用Swern等人在Org.Synth.,(1963)43,93-96和美国专利3,180,886上所述的标准步骤进行。通常完全溶于甲磺酸的二酯或二酸,可用室温下的6-9mol当量的70%至90%的过氧化氢处理3-5小时。从芳族羧酸酯转化为过酸的转化率可达60-80%或更高;脂族酯的转化率通常更成功,为90%或以上。
当加入洗涤剂组合物使用时,本发明的酰氨基过氧酸的浓度范围为约1至约40%,优选为约1.5-约15%,最佳为约2-约5%(重量)。
含有按照本发明的过氧酸漂白体系的洗涤组合物中,也通常含有表面活性剂和洗涤助剂。当液态时,表面活性剂不仅作为洗涤用,而且起着将水不溶性酰氨基过氧酸悬浮于水中或任何其它溶剂载体中,作为结构体系的重要作用。对于重油洗涤液,包括一种pH调节体系和一种抗絮凝聚合物也是重要的。
表面活性物质可以得自天然,如皂,或选自阴离子、非离子、两性离子、阳离子活性物质或其混合物的一种合成物质。许多合适的活性物质可来自商品,并已在文献中充分描述,例如,Schwartz、Perry和Berch的“Surface Active Agents and Detergents”第Ⅰ和Ⅱ卷。表面活性物质的总含量可高达组合物重量的50%,优选约1%-约40%,最好优选4-25重量%。
合成的阴离子表面活性剂通常是水溶性的有机硫酸盐和磺酸盐的碱金属盐,它们具有含约8至约22个碳原子的烷基部分,这里的烷基的含义也包括较高级芳基的烷基部分。
合适的阴离子洗涤化合物的实例是烷基硫酸钠和铵,尤其是由如从牛油或椰子油产生的较高级(8-18碳)醇硫酸盐化得到的那些;烷基(9-20碳)苯磺酸钠和铵,尤其是线性仲烷基(10-15碳)苯磺酸钠;烷基甘油醚硫酸钠,尤其是来自牛油或椰子油的较高级醇和来自石油的合成醇的那些醚;椰子油脂肪酸单甘油酯硫酸钠和磺酸钠;较高级(9-18碳)脂肪醇-烯化氧特别是环氧乙烷的反应产物的硫酸酯的钠盐和铵盐;脂肪酸,如用羟乙磺酸酯化的并用氢氧化钠中和的椰子脂肪酸的反应产物;甲基牛磺酸的脂肪酸酰胺的钠盐和铵盐;烷基磺酸盐,如由α烯烃(8-20碳)与二亚硫酸钠反应产生的那些,和由石蜡烃与SO2和Cl2反应产生的那些,以及然后用碱水解产生的无规磺酸盐;二烷基磺基琥珀酸钠和铵;以及烯烃的磺酸盐,烯烃的磺酸盐用来描述由烯烃,尤其是10-20碳的α-烯烃与SO3反应,然后中和和水解反应产物制得的物质。优选的阴离子洗涤化合物是11-15碳烷基苯磺酸钠;16-18碳烷基硫酸钠和16-18碳烷基醚硫酸钠。
可优选用于与阴离子表面活性化合物一起使用的合适的非离子表面活性化合物,包括特别是烯化氧,通常是环氧乙烷与烷基(6-22碳)苯酚的反应产物,通常为2-25EO,即每分子中含2-25个环氧乙烷单元;脂族(8-18碳)伯或仲、线性或分支醇类与环氧乙烷的缩合产物,通常2-30EO,以及环氧乙烷与由环氧丙烷和亚乙基二胺的反应产物的缩合产物。其它所谓的非离子表面活性物质包括烷基多苷,长链叔胺氧化物,长链叔膦氧化物和二烷基亚砜。
两性表面活性化合物也可用于本发明的组合物,但由于它们的成本较高,一般不需要用。如果使用任何两性洗涤化合物,则它们相对于通常大量使用的合成阴离子和非离子活性剂而言,在组合物中其用量很小。
本发明的洗涤组合物通常也含有一种洗涤助剂。助洗剂物质可选自(1)钙螯合剂,(2)沉淀物质,(3)钙离子交换物质和(4)它们的混合物。
具体来说,本发明的组合物可含有任何一种有机或无机助洗剂,如三聚磷酸钠或钾、焦磷酸钠或钾、正磷酸钠或钾、碳酸钠、次氮基三乙酸的钠盐,柠檬酸钠、羧甲基马来酸盐、羧甲氧基琥珀酸盐、酒石酸盐、单和双琥珀酸盐、氧基二琥珀酸盐、结晶或无定形硅铝酸盐和它们的混合物。
多羧基均聚或共聚物也可包括在助洗剂中,并起粉末结构剂或加工助剂的作用。特别优选的是聚丙烯酸(可从Rohm and Haas Compang买到商标为Acrysol的商品)和丙烯酸-马来酸共聚物(可从BASF Corporation买到商标为Sokalan的商品)和其碱金属或其它金属的盐。
钙离子交换助洗剂的实例包括各种类型的水不溶结晶的或无定形硅铝酸盐,其中沸石是最熟知的代表性物质,如沸石A、沸石B(也称为沸石P)、沸石C、沸石X、沸石Y和EP-A-0 384 070中描述的沸石P。
这些助洗剂可以例如1-80wt%,最好10-60wt%的含量存在。
在洗涤水中分散后,过氧酸的起始量应以如下量使用,即能使每升水的各处产生约0.05至约250ppm活性氧,最好约1-50ppm活性氧。洗涤水中存在的表面活性剂可以每升水0.05-1.0g,最好0.15-0.20g的量存在。当存在时,助剂的量为每升水0.1-3.0g。
对于重油洗涤液,使用一种pH调节体系,已知为pH“跃变体系”是有利的。众所周知,有机过氧酸漂白剂在低pH(3-6)下最稳定,而在弱碱性pH(7-9)溶液中作为漂白剂最有效。为了达到所需的pH,可应用一个pH跃变体系,使得为了过酸的稳定性时调低pH,在洗涤水中作漂白和洗涤用时,将其调高到弱碱性。一个这种体系是硼砂:10H2O/多元醇。硼酸根离子和某些顺-1,2-多元醇在浓缩时络合而形成较低的pH。在稀释时,该络合物离解,放出游离硼酸根而升高pH。能与硼酸根起这种络合作用的多元醇包括儿茶酚、半乳糖醇、果糖、山梨醇和颇哪醇。从经济上考虑,优选山梨醇。为了实现所需的浓缩pH(<6),通常需要多元醇与硼砂的比例大于1∶1。
因此,通常需要优选比例的硼砂。优选的多元醇与硼砂之比是各处均达约1∶1至约10∶1。含硼酸根的化合物,如硼酸、氧化硼、硼砂以及正或焦硼酸钠也可适于作硼酸根组分。优选的pH跃变体系是以1-40wt%的量存在于组合物中。
本发明的重油液体洗涤组合物中的另一有用组分是抗絮凝聚合物。亲水和憎水单体的共聚物常用于形成该抗絮凝剂。合适的聚合物是由下列物质,如马来酸酐、丙烯酸或甲基丙烯酸或其它亲水单体如乙烯磺酸盐或苯乙烯磺酸盐等与已经用憎水基团功能化了的相似单体共聚而获得的。这些包括酰胺、酯类、脂肪醇的醚或脂肪醇乙氧基化物。除脂肪醇和其乙氧基化物外,其它憎水基团,如烯基或烷芳基也可使用。重要的是该共聚物要具有可接受的氧化稳定性、与薄液滴相互作用的憎水基团和结构液体的亲水基团,以防止这些液滴的絮凝,因而可防止物理不稳定性和产物的分离。在实践中,丙烯酸和甲基丙烯酸月桂酯(M.W.3800)的共聚物已发现在0.5-1%的水平是有效的。这些物质在美国专利4 992 194(Liberati等人)中已充分描述过,在这里引为参考。
除已提及的组分外,本发明的洗涤组合物,可含有任何一种常规添加剂,其量为在洗涤组合物中常用量。
这些添加剂包括增泡剂,如链烷醇酰胺,特别是从棕榈仁脂肪酸和椰子脂肪酸制得的单乙醇胺,降泡剂,如烷基磷酸酯和硅氧烷,抗再沉积剂,如羧甲基纤维素钠和烷基或取代的烷基纤维素醚,其它稳定剂,如乙二胺四乙酸,织物柔软剂,无机盐,如通常以极小量存在的硫酸钠,荧光增白剂,香料、酶,如淀粉酶、蛋白酶和脂肪酶,抗菌剂及着色剂。
这里描述的酰氨基过氧酸在一系列洗涤产品中是有用的。这些包括洗衣洗涤剂、洗衣漂白剂、硬表面清洗剂、厕所水池清洁剂、自动洗碟组合物以及甚至牙科清洗剂。本发明的过氧酸可以引入一系列产品形式中,包括粉末中、板上或其它底物上,装在袋中,做成小片或在非水液体,如液体非离子洗涤剂中。
下列非限制性实例将更充分说明本发明的实施方案。说明书和权利要求中的所有份数、百分数和比例均以重量表示,除非另有说明。
实例1
对苯二酸一甲基一钾
在室温下将溶于870ml甲醇的87.5%KOH(143g,2.24mol)在45分钟内加入溶于2420ml甲苯的对苯二酸二甲酯(434g,2.24mol)中。将反应混合物在65℃搅拌下加热3小时,然后使之冷却至室温。用3500ml温甲苯洗涤过滤所得固体,干燥产生464.08g(95%产率)的白色固体。IR(nujol)1735,1600,1550,1410,1290,730cm-1。
N,N′-二(4-羰甲氧基苯甲酰基)哌嗪
将对苯二酸-甲基-钾(175.8g,0.8056mol)悬浮于5升三颈瓶内的甲苯(2000ml)中,三颈瓶装有一上方搅拌器、冷凝器和加料漏斗。逐滴将亚硫酰氯(58.76ml,0.8056mol)加入快速搅拌着的悬浮液中,并将混合物加热至67℃,保持3小时。在室温下搅拌过夜,反应产物经硅藻土床的布氏漏斗过滤,保留含4-羰甲氧基苯甲酰氯的滤液。这时,该酰氯可由加入一等体积***分离,过滤出氯化钾副产品,在真空中除去溶剂。大多数步骤中直接使用甲苯溶液。
将碳酸钾(266.2g,1.61mol)和哌嗪(34.69g,0.4027mol)溶于盛在5升Morton烧瓶内的1000ml的水中。在瓶内反应温度保持在25℃下,逐滴加入4-羰甲氧基苯甲酰氯的甲苯溶液。将混合物搅拌过夜,过滤,用甲苯、水、1N HCl和水先后洗涤,得到127g(77%)N,N′-二(4-羰甲氧基苯甲酰基)哌嗪白色固体。
mp.234-237℃;IR(nujol)1730,1630,1610,1510,1290,1260,1010,730cm-1.
1H NMR(200MHz,CDCl3/CD3COCD3)δ7.48-8.11(8H,m),3.93(6H,s),3.81(4H,br s),3.56(4H,br s);13C NMR(CDCl3/CD3COCD3)δ169.51,166.05,139.19,131.50,129.89,126.98,52.31,43.80,41.10;IR(nujol)2920,2840,1720,1620,1605,1455,1430,1370,1360,1275,1260,1100,1000 cm-1;low res.MS(CI,异丁烷)411(MH+).
N,N′-二(4-过羧基苯甲酰基)哌嗪(PCBPIP)
N,N′-二(4-过羧基苯甲酰基)哌嗪(4.07g,0.0099mol)溶于甲磺酸(14ml)中,用0℃的过氧化氢(3.37ml,70%的溶液,0.0891mol)处理之。在室温下搅拌混合物5小时,然后倒在冰-水上。将固体收集在布氏漏斗上,用水洗至pH为5,空气干燥过夜。产生3.91g(95%)白色粉末;熔点268(熔融前分解)。碘法滴定指示为65%的过酸。IR(nujol)3100(羟基),1760((过酸羰基)cm-1。
实施例2
N.N′-二(4-羰甲氧基苯甲酰基)亚乙基二胺
使用制N,N′-二(4-羰甲氧基苯甲酰基)哌嗪所述步骤,用亚乙基二胺(26.9ml,0.4028mol)代替哌嗪,用400ml水而不用1000ml水进行制备。产生88.6g(57%)产物。
mp.297-299℃;1H NMR(200 MHz,DMSO-d6)δ8.82(2H,br s),8.06-7.94(8H,m),3.88(6H,s),3.47(4H,s);IR(nujol)3300,1730,1640,1550 cm-1.
N,N′-二(4-过羧基苯甲酰基)亚乙基二胺(PCBED)
N,N′-二(4-羰甲氧基苯甲酰基)亚乙基二胺(0.5g,0.0129mol)溶于30ml甲磺酸中,用0℃的过氧化氢(4.4ml 70%的溶液)处理。让混合物升至室温,并搅拌5小时。将溶液倒在冰和饱和的硫酸铵上,过滤固体,用水洗涤至pH5。用碘量滴定法测得活性成分为78%。
实例3
N,N′-二(4-羰甲氧基苯甲酰基)-1,4-亚苯基二胺
将溶于氯仿(95ml)的4-羰甲氧基苯甲酰氯(9.32g,0.046mol)加入4℃的溶于三乙胺(4.81ml,0.035mol)和氯仿(250ml)的1,4-亚苯基二胺(2.59g,0.023mol)中。使反应物温热至室温,过夜。在真空中除去氯仿。将固体倒到冷的5%HCl上,过滤,用稀HCl洗涤。用DMF再结晶,产生6.16g(62%)的浅黄色粉末,熔点>345℃
1H NMR(DMSO-d6)δ8.06(8H,s),7.74(4H,s),3.88(6H,s);13C NMR(H2SO4/CD3COCD3)(dec.to acid)δ205,196,169.77,167.10,132.56,130.95,128.16,127.79,127.03,122.85,119.82,52.02;IR(nujol)3330,2900,2840,1720,1640,1550,1455,1410,1375,1280,1190,1110 cm-1;low res.MS(CI,异丁烷)433(MH+),271,257,223.
N,N′-二(4-过羧基苯甲酰基)亚苯基二胺(1,4-PCBPD)
N,N′-二(4-羰甲氧基苯甲酰基)亚苯基二胺(3.07g,0.0071mol)溶于甲磺酸(40ml)并用室温的过氧化氢(2.42ml 70%的溶液,0.0639mol)处理。室温下搅拌6小时,将反应保持在3℃达12小时。将混合物倒在冰-饱和硫酸铵溶液上,然后如前法分离之,得到1.85g(59%)橘色粉末,m.p.>315℃。碘量滴定指示为60%过酸。IR(nujol)3230(羟基),1755(过酸羰基)cm-1。
实例4
N,N′-二(4-羰甲氧基苯甲酰基)-1,4-二氨基环己烷
4-羰甲氧基苯甲酰氯(9.057g,0.0456mol)溶于500ml装有机械搅拌器和加料漏斗的三颈烧瓶内的氯仿(180ml)中。向此溶液中在30分钟内加入0℃的反-1,4-二氨基环己烷(2.60g,0.0228mol)、三乙胺(7.5ml,0.0535mol)和氯仿(80ml)。搅拌下反应2.5小时,过滤产物除去氯仿。用10%HCl和饱和NaCl水溶液洗涤湿固体。将产物溶于0℃浓硫酸中,破碎冰水得到白色粉末,产率的80%,m.p.>350℃。1H NMR(200MHz,D2SO4)δ8.30-7.94(8H,m),4.27-4.37(8H,m),2.34-1.80(8H,br m),13C NMR(200 MHz,H2SO4/CD3COCD3)δ170.92,132.32,129.92,129.25,127.61,55.04,51.83,24.07;IR(nujol)3295,2920,2850,1720,1630,1530,1460,1375,1285 cm-1.
N,N′-二(4-过羧基苯甲酰基)-1,4-二氨基环己烷(PCBHEX)
N,N′-二(4-过羧基苯甲酰基)-1,4-二氨基环己烷(1.63g,0.0037mol)溶于甲磺酸(10ml)中,用室温过氧化氢(1.26ml 70%的溶液,0.0333mol)处理。7小时后用冰水结束反应,在25℃真空炉内干燥,得到1.57g(95%)的白色粉末;m.p.>310℃。碘量滴定指示为79%过酸。1H NMR(200MHz,DMSO-d6)δ8.47-8.44(m,酯),8.03-7.91(m,过酸和酯),3.88(s,酯),3.79(br s,酯和过酸),1.94-1.91(m,酯和过酸),1.52-1.43m,酯和过酸);IR(nujol)3295(宽,羟基),1730(过酸羰基)cm-1。
实例5
羰乙氧基己二酰氯
己二酸一乙基酯(25.63g,0.147mol)与亚硫酰氯(34.98g,0.293mol)在圆底烧瓶内反应,烧瓶装有冷凝器,加热到37℃保持3小时。用改型蒸馏头代替冷凝器,在5mmHg下除去过量亚硫酰氯。蒸馏出透明液体(59℃/约0.1mmHg)产物(26.84g,95%)。IR3550,3420,2950,2910,2840,1785,1715,1455,1360,1230,1170,1140,1080,1010,940cm-1。
N,N′-二(羰乙氧基己二酰基)-1,4-亚苯基二胺
羰乙氧基己二酰氯(13.74g,0.071mol)于氯仿(40ml)中的溶液被加入4℃的1,4-亚苯基二胺(3.89g,0.036mol)于氯仿(330ml)和三乙胺(7.53ml,0.054mol)的溶液中。5小时内将反应介质温热至室温。用乙酸乙酯对其结晶,得到6.30g(42%)白色蓬松固体;
m.p.156-160℃.1H NMR(DMSO-d6)δ9.81(2H,s,NH),7.49(4H,s),4.04(4H,q),1.57(8H,m),2.34(8H,m),1.18(6H,t);13C NMR δ 173.65,171.25,134.38,120.74,60.39,36.90,33.98,25.01,24.42,14.23;IR(nujol)3290,2920,2840,1720,1645,1540,1455,1370,1370,1290,1255,1170 cm-1;low res MS(CI,异丁烷)421(MH+).
N,N′-二(过羧基己二酰基)亚苯基二胺(DPAPD)
N,N′-二(羰乙氧基己二酰基)-1,4-亚苯基二胺(6.00g,0.0143mol)溶于甲磺酸(21ml),用室温过氧化氢(4.87ml 70%的溶液,0.1287mol)处理。2小时后从冰水中分离产物,得到4.97g(88%)浅橘色粉末;m.p.210-212(分解)。碘量滴定指示为87%过酸。1HNMR(200 MHz,DMSO-d6)δ11.97(2H,br,s),9.83(2H,s)7.49(4H,m),4.10(trace,q,酯),2.49-2.00(8H,m),1.57(8H,br s),1.17 trace,t,酯);IR(nujol)3100(羟基),1750(过酸羰基)cm-1.
实施例6
N,N′-(4-羰甲氧基苯甲酰基)-1,4-丁二胺
将4-羰甲氧基苯甲酰氯(19.07g,0.096mol)溶于置于装有机械搅拌器、温度计和加料漏斗的1000ml圆底烧瓶内的甲苯(380ml)中。在40分钟内逐滴向烧瓶内加入1,4-丁二胺于水中的溶液(80ml),同时由水浴保持反应混合物的温度在25℃。立即形成白色固体,再搅拌反应混合物2小时。将固体收集在烧结玻璃上,分别用甲苯、水、5%HCl和水洗涤。用DMF再结晶,得到白色晶体,在真空炉内60℃下干燥,产品17.91g(90%),熔点
260-261℃.1H NMR(200MHz,DMSO-d6)δ8.70(2H,m),8.05-7.93(8H,m)3.88(6H,s),3.34(4H,s),1.58(4H,s);IR(nujol)3300,1720,1625,1530,1275,1105,860,730 cm-1;low res.MS(CI,异丁烷)413(MH+);13C NMR(75MHz,DMSO-d6)δ166.9,165.7,165.4,165.2,138.7,131.6,129.0,127.5,127.2,52.3,26.5.
N,N′-二(4-过羧基苯甲酰基)-1,4-丁二胺(PCBBD)
溶在甲磺酸(25ml)内的N,N′-二(4-羰甲氧基苯甲酰基)-1,4-丁二胺(3.00g,0.007mol)由上述方法用过氧化氢(2.50ml 70%)的溶液,0.066mol)处理。室温下5小时,3℃16小时后,使过酸在冰上沉淀,用水洗涤,干燥得到1.8g(60%)的白色粉末;m.p.180℃(分解)。碘量法滴定表明为74%过酸,5.7%a.o.(理论上:7.7% a.o.)。IR(nujol)3320-3100(羟基),1745(过酸羰基)cm-1;1H NMR(200MHz,DMSO-d6)δ8.65(2H,m),8.03-7.90(8H,m),3.87(st 起始原料,7%),3.29(4H,s),1.58(4H,s).
实例7
N,N′-二(4-羰甲氧基苯甲酰基)-1,2-亚苯基二胺
4-羰甲氧基苯甲酰氯(18.5g,0.093mol)在氮气下溶于氯仿(100ml),冷却到0℃。逐滴向其中加入1,2-亚苯基二胺(5.00g,0.046mol)和三乙胺(12.8ml,0.092mol)于氯仿(350ml)中的溶液。16小时后,用带滤纸的烧结玻璃过滤除去氯化三乙基铵。用冷的5% HCl(3×200ml)和饱和的NaCl溶液(2×150ml)洗涤有机层,用硫酸镁干燥之。减压下除去氯仿分离得产物。用乙醇再结晶,得到12.19g(61%)白色粉末;m.p.211-216℃。
1H NMR(200 MHz,DMSO-d6)δ10.24(2H,s),8.09-8.07(8H,2s),7.69(2H,s),7.33(2H,s),3.90-3.88(6H,2s);13C NMR(50 MHz,DMSO-d6)δ165.29,164.37,138.13,131.82,130.94,128.94,127.69,125.79,125.42,52.08;IR(nujol)3380,3280,1720,1645,1540,1290,1275,1100 cm-1;low res.MS(CI,异丁烷)433(MH+)271,165.
N,N′-二(4-过羧基苯甲酰)-1,2-亚苯基二胺(1,2-PCBPD)
N,N′-二(4-羰甲氧基苯甲酰基)-1,2-亚苯基二胺(2.75g,0.0064mol)溶于甲磺酸(25ml),再冷至0℃。逐滴向其中加入过氧化氢(1.57ml 90%的溶液,0.058mol)。室温下16小时后,如上法结束反应。碘量法滴定表明为70%过酸,5.2% a.o.
(理论值7.3% a.o.)IR(nujol)3160(羟基),1740(过酸羰基)cm-1;1H NMR(200 MHz,DMSO-d6)δ10.20(2H,s),8.09-8.07(8H 2s),7.73-7.52(2H,m),7.39-7.22(2H,m),3.89(ε酯 about 7%);13C NMR(50MHz,DMSO-d6)δ166.58,164.76,137.95,133.37,131.19,129.30,127.76,126.01.
实例8
N,N′-琥珀酰基-二(4-羰甲氧基)苯胺
琥珀酰氯在使用前先在减压下蒸馏。向一个1000ml圆底烧瓶内,在氮气下,使4-氨基苯甲酸甲酯(20g,0.132mol),哌啶(10.7ml,0.133mol)和氯仿(250ml)反应,然后冷至0℃。逐滴向其中加入琥珀酰氯的氯仿溶液(7.5ml,0.068mol)。加入后可观察到淡紫色沉淀。室温2小时后,用烧结玻璃过滤产物,用5%HCl(2×400ml)、水(600ml)依次洗涤,在烧结玻璃上允其空气干燥。用DMF对产物再结晶,在60℃真空炉中干燥,得到16.09g(62%)白色晶体;m.p.284-285℃。
1H NMR 200 MHz,DMSO-d6)δ 10.42(2H,s),7.96-7.74(8H,s),3.85(6H,s),2.75(4H,s);IR(nujol)3340,3320,1710,1690,1675,1610,1595,1530,1295,1270,1175,1160,1105,770 cm-1;low res.MS(CI,异丁烷)385(MH+),234,152;13C NMR(75 MHz,DMSO-d6)δ170.9,165.7,143.6,130.2,123.6,118.2,51.7,31.0.
N,N′-琥珀酰-二(4-过羧基)苯胺(SDPCA)
将N,N′-琥珀酰-二(4-羰甲氧基)苯胺(5.02g,0.013mol)溶于甲磺酸(30ml)中,冷至0℃。逐滴加入过氧化氢(4.43ml 70%的溶液,0.117mol)。室温下6小时后,如常法完成反应,得到淡棕色粉末产物;m.p.201℃。碘量滴定指示为72%过酸,6.0% a.o.(理论8.2% a.o.)。IR(nujol)3200(羟基),1750(过酸羰基)cm-1;1HNMR(200MHz,DMSO-d6)δ10.37,10.34(各2H,s,一个为过酸OH,一个为酰胺-NH),7.92-7.68(8H,m),3.81(s,酯),2.72(4H,s,酯和过酸)。
实例9
N,N′-二(羰乙氧基己二酰基)亚乙基二胺
于水(5ml)中的亚乙基二胺(1.17g,0.0195mol)被逐滴加到室温下的羰乙氧基己二酰氯(2.5g,0.013mol)于甲苯(36ml)的溶液中。再搅拌2.5小时后,过滤白色固体,用甲苯、水、0.1N HCl和水依次洗涤,在63℃真空炉内干燥。在一次消除出现在IR光谱(3080cm-1)的杂质的试探中,在甲苯内提取该物质,用过滤除去不溶物,在真空中除去甲苯得到白色粉末(0.31g,13%);m.p.117-120℃(大部分熔融后留下白色残余物)。
1H NMR(200 MHz,DMSO-d6)δ7.83(2H,br s),4.05(4H,q),3.37(H2O),3.07(5H,br s),2.28-2.02(10H,br s),1.49(9H,br s),1.18(6H,t);相对于乙氧基质子而言,峰在3.07和,1.49处的积分为每处高一个质子,在2.28-2.02处高2个质子。
IR(nujol)3300,2920,2850,1725,1640,1550,1460,1375,1270,1245,1180,730 cm-1.
由于甲苯纯化未能消除未鉴定出的杂质,使用了用于制备N,N′-二(4-羰甲氧基苯甲酰基)哌嗪的方法。羰乙氧基-己二酰氯(1.0g,0.0052mol)于氯仿(12ml)的溶液在氮气下被逐滴加入亚乙基二胺(0.16g,0.0026mol)、三乙胺(0.54ml,0.0039mol)氯仿(5ml)在4℃的溶液中。搅拌混合物5.5小时,如常完成反应,得到0.60g(62%)固体。用甲苯对该产品再结晶得0.20g(21%)仍含由IR和NMR指示的杂质的白色粉末;m.p.120-122℃。用乙酸乙酯也未能消除该杂质。
13C NMR(200 MHz,CDCl3/CD3COCD3)δ207.44,173.87,60.38,40.07,36.08,33.90,25.12,24.39,14.33,14.25;low res.MS(CI,异丁烷)373(MH+).
N,N′-二(过羧基己二酰)亚乙基二胺
N,N′-二(羰乙氧基己二酰)亚乙基二胺(0.023g,0.00055mol)溶于甲磺酸(1.4ml),用室温下的过氧化氢(0.19ml 70%的溶液),并搅拌18小时。该产物难于从冰水中分离出来,它是片状物质(0.0088g,46%),在<220℃时变黑,但低于350℃不熔化。碘量法滴定指示为55%过酸。1H NMR(200MHz,DMSO-d6,δ7.81(br s,酯和过酸),4.10(q,酯),3.06(H2O),2.22和2.19(m,酯和过酸),1.48(m,酯和过酸),1.19(t,酯)。IR(nujol)3200(羟基),1755(过酸羰基)cm-1。
实例10
N,N′-二(4-羧基苯胺)对苯二酸盐
4-氨基苯甲酸(2.1eq,14.11g,0.103mol)和碳酸钠(5eq,25.92g,0.245mol)置于4000ml水中,快速搅拌之。在室温下向其中逐份加入粉末对苯二酰氯。搅拌72小时后,溶液倒于10%HCl上。过滤收集固体,并用水洗涤给出16.6g(83%产率)的白色粉末。该产品内的一种杂质是N-(4-羧基苯甲酰)4-氨基苯甲酸,它是单加成物(<3%)。1H NMR(200 MHz,DMSO-d6)δ10.74(2H,s),8.15-7.90(12H,m),3.4(2H,br s);IR(nujol)3360,1690,1660,1610 cm-1.
N,N′-二(4-过羧基苯胺)对苯二酸盐(DPCAT)
将N,N′-二(4-羧基苯胺)对苯二酸盐(4.98g,0.012mol)悬浮于60ml的甲磺酸中,并用过氧化氢(4.09ml 70%溶液,0.108mol)处理。混合物加热至30℃,保持4.5小时,然后如常法分离。活性91%,6.7% a.o(理论值
7.3% a.o.).IR(nujol)3380,3200,1740,1660,1600 cm-1.
实例11
过酸的漂白性能由对于普通污染,如茶(BC-1)和墨水的清除能力来评价。典型试验是将适当的污染物污染棉花试片(3″×4″),再在40℃含Terg-O-tometer的500ml水洗涤液中洗15分钟。过酸的剂量为10ppm活性氧。
污染的漂白是用一种Colorgard System/05 Reflectometer进行反射测量。漂白由反射量的增加所指示,以△△R报告出来。一般,1个单位△△R在与一个成对比物比较中可察觉出来,2个单位△△R可单独察觉出来。在报告的反射量变化中,由一般洗涤法引起的反射量变化已被计算在内。因而,△△R实际上可被表示为:
△△R=△R过酸+洗涤剂-△R洗涤剂
其中△R是污染织物在洗涤前后的反射量之差
BC-1实验是一式二份进行的,示出的值是平均值。为了保证固体尽可能完全分散,每对BC-1实验之一通常是将过酸预溶解在1ml DMF中,若该值与使用粉末状过酸的实验值相差在1个单元之内,这些值就被平均。在1,2-PCBPD的场合,该值大为不同,因此,溶于DMF内的值在表Ⅱ中被表示在括号内。
墨水污染的漂白是以△B来测量的,△B是Hunter色度计的B-轴上的变化。墨水污染开始是兰的,漂白后褪色,因而增加了△B的值。记录的△△B值是经由洗涤剂对照相伴随进行的去污校正后的△B值。
表Ⅱ
在40℃、10ppm A.O.,P-Surf碱*(1.5g/l)条件下的漂白结果
BC-1△△R INK△△B
PERACID | pH8 | pH9 | pH10 | pH9 |
PCBBD | 9.5 | 9.4 | 6.0 | 28.9 |
1,2-PCBPD | 4.4(8.1) | 4.1(6.5) | 3.9 | 24.9 |
SDPCA | 2.7 | 3.3 | 5.0 | 16.8 |
PCBED | 10.6 | 9.0 | 5.9 | 19.1 |
DPAPD | 7.1 | 6.7 | 4.0 | 8.0 |
PCBPIP | 3.0 | 2.9 | 3.1 | 9.7 |
PCBHEX | 0.9 | 2.1 | 3.1 | 4.2 |
DPCAT | 1.6 | 1.5 | 2.3 | 3.1 |
*P-Surf碱的配方:
33%三聚磷酸钠,28%硫酸钠,16%线性烷基苯磺酸盐
15%碳酸钠,0.9%次要成分,加水至100%。
实例12
差分扫描量热法(DSC)
新的过酸的热敏感性的良好指示器是它们对快速加热的响应。表Ⅲ含有从DSC分析得到的数据。所用的仪器是杜邦的DSC,它带有2910电池盘及2100热分析器。将约1mg样品准确称重放入带涂层的铝盘内,然后将其半密封。平衡到30℃,将样品加热,速率5℃/分。
表Ⅲ DSC结果
样品 | 开始自加热温度(℃) | 释放的能量Cal g-1 Kcal mol-1 | mpt(℃) | |
PAP | 87 | 118 | 33 | 92 |
DPDA | 96 | 366 | 96 | 96-99 |
1,2-PCBPD | 130 | 238 | 104 | |
DPAPD | 137 | 291 | 115 | 210(dec) |
DPCAT | 140 | 277 | 121 | |
SDPCA | 150 | 317 | 123 | |
PCBPIP | 160 | 326 | 135 | 268(dec) |
PCBHEX | 175 | 246 | 109 | >310 |
PCBED | 174 | 294 | 114 | 178(dec) |
SBPB | 178 | 354 | 120 | >290 |
*校正到100%过酸含量。误差为5%或更低。
所有新的过酸在超过130℃时均有“开始发动”(onset)的温度。这些高的发动温度表明其有好的热稳定性,并为本发明的目的之所需。对本发明目的而言,过酸具有至少100℃的发动温度是有利的,优选约100-400℃,更优选120°-250℃,最佳为约120°-200℃。
实例13
在重油洗涤液中过酸的稳定性
本研究中所用的组合物中含35%表面活性剂和pH4.5。该pH是由一硼砂/山梨醇pH跃变体系所获得。测得洗涤水中过酸给出5ppm a.o.(约为组合物的2wt%)。该组合物贮存在40℃,并周期性地逐份取出,并滴定剩余的过酸的百分数。
表Ⅳ 在重油洗涤液中过酸的稳定性
过酸 t1/2AT 40℃(天) | |
PCBPIP | 79 |
DPCAT | 65 |
SDPCA | 43 |
PCBED | 34 |
1,2-PCBPD | 33 |
DPAPD | 32 |
PCBBD | 15 |
SBPB | 11 |
DPDA | 5 |
PAP | 3 |
在重油洗涤液中发现所有新的过酸比DPDA和PAP稳定得多。其中5个的半寿命期超过30天。PCBPIP在40℃的半寿命期长达79天。
对于本发明的目的而言,实现过氧化物稳定性在40℃时的半寿命期至少10天,优选至少15天,更优选至少30天,最好超过50天是有利的。
Claims (9)
3、根据权利要求1的过氧酸,选自:
N,N′-二(4-过羧基苯甲酰)-1,4-丁二胺;
N,N′-二(4-过羧基苯甲酰)-1,2-亚苯基二胺;
N,N′-琥珀酰-二(4-过羧基)苯胺;
N,N′-二(4-过羧基苯甲酰)亚乙基二胺;
N,N′-二(4-过羧基苯甲酰)哌嗪;
N,N′-二(4-过羧基苯甲酰)-1,4-二氨基环己烷;
N,N′-二(4-过羧基苯甲酰)-1,4-亚苯基二胺;
N,N′-二(过羧基己二酰)亚苯基二胺;
N,N′-二(过羧基己二酰)亚乙基二胺;和
N,N′-二(4-过羧基苯胺)对苯二酸盐。
4、根据权利要求1的过氧酸,在40℃时具有至少10天的过氧化物半寿期。
5、根据权利要求4的过氧酸,在40℃时具有至少30天的过氧化物半寿期。
6、根据权利要求1的过氧酸,具有至少100℃的自加热开始发动温度。
7、根据权利要求6的过氧酸,具有约120℃-200℃的自加热开始发动温度。
9、一种洗涤组合物,包括:
ⅰ)按照权利要求1的酰氨基过氧酸化合物,其量为约1-40wt%;
ⅱ)表面活性剂,其量为约1-50wt%;和
ⅲ)pH跃变体系,其量为约1-40wt%。
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-
1992
- 1992-03-31 US US07/860,849 patent/US5268003A/en not_active Expired - Fee Related
-
1993
- 1993-03-26 AU AU35494/93A patent/AU651926B2/en not_active Ceased
- 1993-03-29 MX MX9301751A patent/MX9301751A/es unknown
- 1993-03-29 KR KR1019930004926A patent/KR930019619A/ko not_active Application Discontinuation
- 1993-03-29 CA CA002092862A patent/CA2092862A1/en not_active Abandoned
- 1993-03-30 DE DE69300436T patent/DE69300436T2/de not_active Expired - Fee Related
- 1993-03-30 ES ES93302492T patent/ES2078801T3/es not_active Expired - Lifetime
- 1993-03-30 EP EP93302492A patent/EP0564251B1/en not_active Expired - Lifetime
- 1993-03-30 CN CN 93103395 patent/CN1078719A/zh active Pending
- 1993-03-30 BR BR9301372A patent/BR9301372A/pt not_active IP Right Cessation
- 1993-03-31 JP JP5074310A patent/JPH06100531A/ja active Pending
- 1993-03-31 ZA ZA932318A patent/ZA932318B/xx unknown
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104350154A (zh) * | 2012-03-30 | 2015-02-11 | 纳幕尔杜邦公司 | 对于过酸的生产有用的酶 |
CN104364384A (zh) * | 2012-03-30 | 2015-02-18 | 纳幕尔杜邦公司 | 对于过酸的生产有用的酶 |
CN104364384B (zh) * | 2012-03-30 | 2018-12-28 | 纳幕尔杜邦公司 | 对于过酸的生产有用的酶 |
CN104350154B (zh) * | 2012-03-30 | 2020-12-29 | 纳幕尔杜邦公司 | 对于过酸的生产有用的酶 |
Also Published As
Publication number | Publication date |
---|---|
DE69300436T2 (de) | 1996-02-29 |
AU651926B2 (en) | 1994-08-04 |
CA2092862A1 (en) | 1993-10-01 |
EP0564251A3 (en) | 1993-10-27 |
KR930019619A (ko) | 1993-10-18 |
ZA932318B (en) | 1994-09-30 |
MX9301751A (es) | 1993-10-01 |
EP0564251A2 (en) | 1993-10-06 |
EP0564251B1 (en) | 1995-09-06 |
JPH06100531A (ja) | 1994-04-12 |
AU3549493A (en) | 1993-10-07 |
BR9301372A (pt) | 1993-10-13 |
US5268003A (en) | 1993-12-07 |
DE69300436D1 (de) | 1995-10-12 |
ES2078801T3 (es) | 1995-12-16 |
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