CN1220659A - N-双-或n-三-[(1,2-二羟基-乙氧基)-乙基]胺衍生物以及它们的制备和用途 - Google Patents
N-双-或n-三-[(1,2-二羟基-乙氧基)-乙基]胺衍生物以及它们的制备和用途 Download PDFInfo
- Publication number
- CN1220659A CN1220659A CN97195135.7A CN97195135A CN1220659A CN 1220659 A CN1220659 A CN 1220659A CN 97195135 A CN97195135 A CN 97195135A CN 1220659 A CN1220659 A CN 1220659A
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- CN
- China
- Prior art keywords
- compound
- formula
- ethyl
- acid
- alkaline
- 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
Links
- -1 1,2-dicarboxy-ethoxy Chemical group 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002738 chelating agent Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- 239000003352 sequestering agent Substances 0.000 claims description 21
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 235000014347 soups Nutrition 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000004061 bleaching Methods 0.000 claims description 12
- 229910052728 basic metal Inorganic materials 0.000 claims description 10
- 150000003818 basic metals Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 229960004418 trolamine Drugs 0.000 claims description 6
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- 235000003704 aspartic acid Nutrition 0.000 claims description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 150000003456 sulfonamides Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 239000003206 sterilizing agent Substances 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 2
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 description 34
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 10
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 8
- 150000004702 methyl esters Chemical class 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical group OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 125000001181 organosilyl group Chemical class [SiH3]* 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000011122 softwood Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229960005261 aspartic acid Drugs 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 150000002604 lanthanum compounds Chemical class 0.000 description 3
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 108010011485 Aspartame Proteins 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000010934 O-alkylation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- IAOZJIPTCAWIRG-QWRGUYRKSA-N aspartame Chemical compound OC(=O)C[C@H](N)C(=O)N[C@H](C(=O)OC)CC1=CC=CC=C1 IAOZJIPTCAWIRG-QWRGUYRKSA-N 0.000 description 2
- 239000000605 aspartame Substances 0.000 description 2
- 229960003438 aspartame Drugs 0.000 description 2
- 235000010357 aspartame Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000931705 Cicada Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XCOBLONWWXQEBS-KPKJPENVSA-N N,O-bis(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)O\C(C(F)(F)F)=N\[Si](C)(C)C XCOBLONWWXQEBS-KPKJPENVSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical class [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 239000012063 pure reaction product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000005144 thermotropism Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/037—Stabilisation by additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
-
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Abstract
本发明涉及具有式(Ⅰ)的N-双-或N-三-[(1,2-二羧基-乙氧基)乙基]胺衍生物,其中R为H,(a)或(b),且R2为氢,碱金属或碱土金属。本发明还涉及制备上述化合物的方法以及它们作为螯合剂的用途。
Description
本发明涉及新的N-双-或N-三-[(1,2-二羧基-乙氧基)-乙基]胺衍生物以及它们的制备和用途。
例如在各种洗涤过程中,经常需要结合重金属离子和碱土金属离子作水溶性螯合剂。在摄影化学中,金属离子螯合剂被用作显影剂。
当氧化物或过氧化物被用于浆状物的整个无氯(TCF)漂白时,很重要的一项工作是要在漂泊前,除去纤维中的重金属,原因是重金属盐催化过氧化物的分解并形成游离基化合物。这些反应的结果是破坏了纤维的强度特性。
目前,最常用于上述应用中的复合剂是乙二胺四乙酸(EDTA)及其盐,以及二亚乙基三胺五乙酸(DTPA)及其盐。这些都是极好的复合剂,但它们的生物降解能力极差。
专利申请FI-960758,FI-960757,FI-960756和FI-960755公开了天冬氨酸衍生物作为螯合剂在浆状物漂白中的用途。这些螯合剂包括乙二胺二琥珀酸(EDDS)及其碱土金属盐,以及N’,N-亚氨基二琥珀酸(ISA)及其碱土金属盐。EDDS以及ISA是有效的重金属螯合剂,另外它们可以生物降解。
从日本专利申请7261355以及6282044中得知了EDDS型的天冬氨酸衍生物,其中的烃链要比EDDS中的长。其中的一个物质是N,N’-(氧二-2,1-乙二基)-双-L-天冬氨酸。
螯合剂中应含有尽可能少量的氮以便使进入废水中的氮尽量少。日本专利申请7120899以及7120894中报道了EDDS类型的螯合剂,其中的部分氮原子被氧原子所取代。这些专利申请中还公开了各种N-[2-(1,2-二羧基乙氧基)-乙基]天冬氨酸(EDODS)异构体在摄影化学中的用途。根据该公开,EDODS是可以生物降解的。文献(J.vanVestrenen et al.Recl.Trav.Chem.Pays-Bas,vol.109,1990,p.474-478)中报道了通过La3+-催化的马来酸盐的O-烷基化来制备EDODS的方法。但是在申请者进行的申请试验中却证明,EDODS并不是一个十分有效的螯合剂。对于这种不甚理想的螯合结果,有一种可能解释就是由于二羧乙基基团之间碳链的长度。如果所说的碳链不够长,在复合过程中分子产生了张力,金属复合物就不够稳定。
本发明的目标是要开发有效的螯合剂,其可以生物降解并含有尽可能少量的氮。
在所述的分子结构中,伯或叔氮原子作为中心原子。另外,分子结构含有四或六个羧酸基团,其可有效地与重金属协调。碳链足够长以便可以形成有利的键角。
根据本发明,新的化合物包括N-双-[(1,2-二羧基-乙氧基)乙基]胺(BCEEA),N-三-[(1,2-二羧基-乙氧基)乙基]胺(TCEEA),N-双-[(1,2-二羧基-乙氧基)乙基]天冬氨酸(BCEEAA),以及上述化合物的碱金属和碱土金属盐,优选Na+,K+,Ca2+,和Mg2+盐。TCEEA
BCEEA
BCEEAA
根据本发明,新的胺类化合物可按下法制备:按照合成路线1,并在镧化物或碱土金属催化剂的存在下,采用作为起始物的马来酸的碱金属和碱土金属盐以及二乙醇胺或三乙醇胺。合成路线ⅠR=HR’-CH2CH2OHM=Na+,K+,Li+,Mg2+,Ca2+
在合成中作为作为中间步骤的马来酸盐可在水溶液中制备,优选采用并有市售的物质来作为起始物质,如马来酸酐和碱金属或碱土金属化合物。适于反应的碱金属化合物包括氢氧化锂,氢氧化钠,氢氧化钾,碳酸钠,碳酸钾以及碳酸锂的反应。适于反应的碱土金属化合物包括氢氧化镁,氧化镁,碳酸镁,氧化钙,氢氧化钙以及碳酸钙。
马来酸盐的形成是一个放热反应。当马来酸酐被首先加入水中时,形成马来酸。当以合适的速率向其中加入碱时,反应混合物的温度将升至80-90℃,该温度对于进行烷基化反应十分有利。
因此,氨基醇,优选二乙醇胺或三乙醇胺,以及用作催化剂的镧化合物可以迅速地加到碱性的反应混合物中。
镧化合物或其混合物可以用作催化剂。同样,用于O-烷基化的合适的催化剂包括有碱土金属化合物,如氢氧化钙和氢氧化镁。进一步地,镍化合物也可以用作催化剂。
优选采用镧(Ⅲ)化合物,如硝酸镧(Ⅲ),氯化镧(Ⅲ),氧化镧,硫酸镧以及辛酸镧。同样,含有光学活性配体的镧化合物在反应中也可以用作催化剂。
采用La3+-催化的马来酸盐与氨基醇的O-烷基化是一个十分有用的反应,由于是单一步骤的合成,因此催化剂可以再循环使用。在反应结束后,通过用无机酸酸化反应混合物并向热的反应混合物中加入草酸,可以从反应混合物中分离出催化剂。反应混合物的pH值可以用盐酸,硫酸,硝酸或磷酸来调节,优选用盐酸或硫酸。形成的草酸镧沉淀可以通过过滤从反应混合物中分离出来。用硝酸或盐酸对沉淀进行处理,可以将作为催化剂的镧(Ⅲ)盐从草酸盐沉淀中分离出来。处理后的催化剂可以再次使用。
本发明中的化合物还可以用其它方法来制备。
本发明中的化合物特别适用于碱性水溶液,如作为洗涤剂和清洁剂。进一步地,本发明中的化合物特别适合用于摄影化学。
这些新化合物是有用的螯合剂,例如在含有过氧化氢或过氧化物的碱性水溶液中。在用臭氧,过氧化氢或过氧酸如过甲酸,过乙酸,过丙酸或Caro’S酸以及这些酸的联合物对纤维进行漂白之前,这些新化合物在预处理中是特别有用的重金属螯合剂。
由于新化合物不含磷而含有少量氮,比起现时常用的螯合剂来说,他们对环境的污染相当小。
将用下列实例来描述本发明,但其并不限制本发明。实施例1
将29.4g(0.3mol)马来酸酐溶于50ml水中,向反应混合物中加入50g 48%苛性钠溶液(0.6mol NaOH),由此制备马来酸二钠溶液。加入过程中反应混合物的温度保持在70-90℃。将17g(0.05mol)硝酸镧(Ⅲ),La(NO)3×6H2O,与二乙醇胺(10.5g,0.1mol)一起加到反应混合物中。反应混合物于85℃及回流冷凝器下搅拌48小时。冷却反应混合物,用浓硫酸进行酸化(pH1.8)。此后,将反应混合物再次加热到60℃,加入10g草酸和50ml水,反应混合物于60℃下搅拌20分钟,过滤,将形成的草酸镧(Ⅲ)沉淀从热溶液中除去。滤液冷却,过滤除去随后形成的任何沉淀。从剩余的溶液中(40ml)(其含有54%的水),采用13C NMR光谱和质谱,分析出有机化合物为甲硅烷基或甲基酯衍生物
从13C NMR光谱中鉴别出BCEEAA和BCEEA。基于对照光谱鉴别出未反应的起始物质:二乙醇胺和马来酸,以及用于沉淀催化剂的草酸。作为反应的副产物,形成了苹果酸和富马酸;这些都可在对照光谱上鉴别出来。
在定量13C NMR光谱分析的基础上,得到了含有BCEEAA和BCEEA反应混合物(下文中称此混合物为RS12)的组成:
%重量BCEEAA 18.5BCEEA 7.9二乙醇胺 1.2马来酸, 2.2苹果酸 2.5草酸 0.3富马酸 2.1水 54.3Na2SO4 11.0
由于BCEEAA和BCEEA在有机溶剂中的溶解度很差,故不能用1HNMR技术来分析反应混合物。因此对于反应混合物来说,13C NMR光谱分析是很有用的。BCEEAA和BCEEA的13C NMR光谱数据列于表1。
由于在BCEEAA和BCEEA中与氮原子相邻的碳原子的化学位移是不同的,它们的摩尔比例可以通过反应混合物的13C NMR光谱测定出来。BCEEA信号(48ppm)和BCEEAA信号(53ppm)的积分比较显示,BCEEAA∶BCEEA为2∶1。
表1BCEEAA信号 解释说明ppm175 a176 b37.9 c75.8 d65.5 e54.4 f62.0 g32.6 h170.3 i173.9 jBCEEA信号 解释说明ppm175 a176 b37.9 c75.8 d66.4 e47.8 f
为了进行层析,可以采用气相层析中常用的甲硅烷化试剂(BSTFA)对反应混合物进行处理,使含在反应混合物中的羧酸进行甲硅烷化。样品用气相层析-质谱仪进行分析。
柱:J&W DB5 30m,1.0μm膜,0.32mm i.d.
温度程序:80 ℃---->320℃,10℃/分钟
注射口温度:250℃
借助质谱,在分子断裂的基础上,可以确定BCEEA和BCEEAA的分子结构。上述化合物的甲硅烷衍生物的结构以及所得到的质谱列于表2。表2BCEEA的甲硅烷衍生物分子量:697m/z(相对强度%):406(20),333(15),245(25),
147(45),73(100)BCEEAA的甲硅烷衍生物分子量:885m/z(相对强度%):678(3),594(20),309(10),245(35),
147(45),73(100)
进一步地,起始物的三甲基甲硅烷衍生物和上述反应的副产物可从质谱中鉴定出来。
在使用三氟化硼作催化剂的反应中,采用甲醇可以使反应混合物中的羧基基团酯化为甲酯。反应副产物的甲酯和BCEEAA的甲酯衍生物可从GC-MS光谱中鉴定出来(表3)。表3BCEEAA的六甲基酯分子量:393m/z(相对强度%):362(30,M-31),302(10),189(10),
113(100),85(55),59(60)
通过离子交换层析将合成中得到的化合物BCEEAA和BCEEA从反应混合物中分离出来,再对所得到的纯反应产物进行分析,可以确定它们的结构。
按照上述所提供的方法,对得到的混合物的样品(13.25g)进行预处理,将1.16g碳酸钙加入其中。存在于样品中的硫酸根离子以硫酸钙的形式沉淀出来。
所使用的离子交换树脂为甲酸盐形式的强阴离子交换树脂(Bio-Rad AGI-X8,200-400目)。使用洗脱液(1000ml)将样品从离子交换柱上洗脱下来;洗脱液中甲酸的浓度呈梯度上升,以使洗脱液中甲酸的浓度在0-2mol/l这个范围内。在洗脱时,搜集到100个10-20ml的样品,用液相层析进行分析。将BCEEA和BCEEAA从馏分中分离出来。通过将纯化并分离的反应产物的光谱数据与从反应混合物中鉴别出来的反应产物的光谱数据进行比较,可以确定反应产物的13C NMR光谱和GC-MS光谱。可以看到纯化的BCEEA和BCEEAA的光谱与列于表1-3中光谱数据一致。实施例2
使用三乙醇胺(1.0mol)以及马来酸酐(3.4mol)作起始原料,按照实施例1所述的方法,可以制备TCEEA。
用13C NMR光谱可以鉴定TCEEA。基于对照光谱,鉴别出未反应的起始物质:三乙醇胺和马来酸,以及用于沉淀催化剂的草酸。作为反应的副产物,形成了苹果酸和富马酸;这些都可基于对照光谱鉴别出来。
在定量13C NMR光谱分析的基础上,得到反应产物的组成如下:
摩尔%TCEEA 46.3三乙醇胺 18.5马来酸, 11.5富马酸 3.2苹果酸 13.5草酸 6.6
在使用三氟化硼作催化剂的反应中,采用甲醇可以使反应混合物中的羧基基团酯化为甲酯。反应副产物的甲酯和TCEEA的甲酯衍生物可从GC-MS光谱中鉴定出来(表5)。表5TCEEA的六甲基酯分子量:581m/z(相对强度):
550(10,M-31),552(5,M-59),406(100,M-175),189(15),172(10),113(30),59(40)实施例3
反应混合物RS12(其组成已在实施例1中进行了描述)可在实验室中制备。pH为9.0的碱性反应混合物可用于氧-去木质化的软材浆状物的洗涤试验,结果列于表4。
为了了解重金属和碱土金属的螯合情况,用上述的水溶液洗涤浆状物。洗涤后,分析洗液中金属的浓度。测定进入洗液中的铁(Fe),锰(Mn),钙(Ca)和镁(Mg)的含量。
就漂白而言,洗液中进入铁和锰有利,相反,洗液中进入钙和镁不利。在对照实验中,用DTPA溶液洗涤浆状物。螯合剂的浓度以及洗涤过程中的pH列于表6。在pH为5.2时,RS12从浆状物中去除锰的有效率同DTPA(为100%),去除铁的有效率为DTPA的83%,去除镁的有效率为DTPA的83%,去除钙的有效率高于DTPA。
表6氧-去木质化的软材硫酸浆状物粘性710 dm3/kg亮度79.7%ISOKappa 6.7
滤液分析 | 正常DTPA=100% | ||||||||||||
时间(分) | T,℃ | 稠度% | 初始pH | 最终pH | 螯合剂kg/tp | Fe,mg/l | Mn,mg/l | Mg,mg/l | Ca,mg/l | Fe% | Mn% | Mg% | Ca% |
60 | 70 | 12 | 未调节 | 1.3 | 1%HNO3 | 1.8 | 0.4 | 80 | 25 | 100 | 133 | 276 | 403 |
60 | 70 | 12 | 5 | 5.4 | DTPA2kg | 1.8 | 0.3 | 29 | 6.2 | 100 | 100 | 100 | 100 |
60 | 70 | 12 | 6.5 | 7.2 | DTPA2kg | 1.7 | 0.3 | 22 | 6.2 | 94 | 100 | 76 | 100 |
60 | 70 | 12 | 5-6 | 5.9 | 水洗 | 0.61 | 0 | 17 | 3.2 | 34 | 0 | 59 | 52 |
60 | 70 | 12 | 5 | 5.2 | RS121.5kg | 1.5 | 0.3 | 25 | 7.2 | 83 | 100 | 86 | 116 |
60 | 70 | 12 | 6.5 | 7.1 | RS121.5kg | 0.8 | 0.3 | 15 | 6.5 | 44 | 100 | 52 | 105 |
实施例4
过氧化氢的分解形成了含有过氧化氢碱性水溶液的一个问题,因此,在重金属(Fe,Mn)(表7)存在下,对实施例1中所描述的含有BCEEAA-和BCEEA-的RS12溶液对于碱性过氧化氢的稳定作用进行了测试。表7碱性过氧化物的稳定性实验条件:pH 10,50℃,H2O2初始浓度5.3g/l
实验序号 | RS12ppm | DTPAppm | EDDSppm | Feppm | Mnppm | H2O2半衰期(分钟) |
1 | 0 | 0 | 0 | 0 | 0 | 530 |
2 | 0 | 273 | 0 | 2 | 4 | 236 |
3 | 0 | 0 | 140 | 2 | 2 | 4 |
4 | 0 | 0 | 280 | 4 | 4 | 2 |
5 | 140 | 0 | 0 | 4 | 2 | 338 |
6 | 140 | 0 | 140 | 0 | 4 | 363 |
7 | 140 | 0 | 280 | 2 | 0 | 226 |
8 | 280 | 0 | 0 | 2 | 4 | 452 |
9 | 280 | 0 | 140 | 4 | 0 | 197 |
100 | 280 | 0 | 280 | 0 | 2 | 1462 |
所用的对照试剂为DTPA,其通常用作铁和锰的螯合剂,例如在浆状物的生产过程中。在本申请预前的实验中已经发现EDDS是一个好的螯合剂,在这里将它作为另一对照试剂。
实验结果显示,RS12明显地比DTPA或EDDS对碱性过氧化氢具有更大的稳定性。因此,含有BCEEAA和BCEEA的溶液可以用作稳定剂,例如在含有过氧化氢的碱性洗涤剂溶液中。
实施例5
对过氧乙酸溶液进行了相应的实验(表8),该实验结果表明,RS12对PAA溶液的稳定作用至少和DTPA一样好。基于这一点,我们所关心的溶液在含有过氧化物的酸性消毒剂中,很适合于用作稳定剂。表8PAA溶液的稳定性实施例反应温度:50℃
实施例6
螯合剂 | ppm | Mnppm | Feppm | pH | PAA的半衰期(分钟) |
无螯合剂 | 0 | 4.8 | 4.5 | 240 | |
DTPA | 140 | 0 | 4.8 | 4.5 | 1339 |
无螯合剂 | 0.4 | 0 | 4.5 | 390 | |
DTPA | 140 | 0.4 | 0 | 4.5 | 4 |
EDTA | 140 | 0.4 | 0 | 4.5 | 7.5 |
RS12 | 140 | 0.4 | 0 | 4.5 | 1005 |
RS12 | 140 | 0 | 4.8 | 4.5 | 647 |
无螯合剂 | 0 | 4.8 | 7 | 87 | |
无螯合剂 | 0.4 | 0 | 7 | 174 | |
DTPA | 140 | 0 | 4.8 | 7 | 201 |
DTPA | 140 | 0.4 | 0 | 7 | 25 |
RS12 | 140 | 0 | 4.8 | 7 | 146 |
RS12 | 140 | 0.4 | 0 | 7 | 229 |
在使用碱性过氧化氢溶液的浆状物漂白中,单独的过氧化物溶液的稳定性无法保证漂白的成功,因此,在软材硫酸浆状物的漂白中,使用含有BCEEAA和BCEEA的RS12溶液。在漂白实验中(表9),将RS12和DTPA作比较,结果显示,当RS12作为螯合剂时,在最终漂白后,浆状物的粘性要好于采用DTPA做螯合剂。Kappa数和亮度在同一水平。值得注意的是,当采用RS12时,本实验溶液中残余过氧化氢是采用DTPA时的2倍,这一结果表明,RS12适合于过氧化物步骤的螯合处理。表9漂白实例处理顺序:氧木质化作用,过氧乙酸木质化作用,螯合,过氧化物的漂白。软材硫酸浆状物氧木质化:Kappa 9.7,粘性775dm3/kgPAA-木质化作用:Kappa 5.3,粘性709dm3/kg螯合步骤
t,分钟 | 60 | 60 | 60 | 60 |
T,℃ | 75 | 75 | 75 | 75 |
pH,初始 | 5 | 6.5 | 5 | 6.4 |
pH,最终 | 5.1 | 6.5 | 5 | 6.2 |
螯合剂 | DTPA | DTPA | RS12 | RS12 |
剂量,kg/tp | 2 | 2 | 1.5 | 1.5 |
最终漂白(碱性过氧化氢)
实施例7
t,分钟 | 180 | 180 | 180 | 180 | 180 |
T,℃ | 90 | 90 | 90 | 90 | 90 |
pH,初始 | 104 | 10.4 | 10.4 | 10.4 | 10.4 |
pH,最终 | 9.7 | 9.8 | 9.8 | 9.8 | 9.5 |
H2O2剂量,kg/tp | 20 | 20 | 20 | 20 | 20 |
残余H2O2kg/tp | 4.1 | 4.1 | 8.9 | 10 | 3 |
残余H2O2,% | 20.5 | 20.5 | 44.5 | 50 | 15 |
Kappa | 2.2 | 2.3 | 2.4 | 2.3 | 2.2 |
粘性,dm3/kg | 553 | 556 | 633 | 644 | 530 |
亮度,%ISO | 85 | 85 | 84.7 | 85.2 | 84.6 |
将29.4g(0.3mol)马来酸酐溶于50ml水中,向反应混合物中加入35.0g氢氧化镁(0.3mol Mg(OH)2)的70ml浆状水溶液,由此制备马来酸镁溶液。加入过程中反应混合物的温度保持在70-90℃。将17g(0.05mol)硝酸镧(Ⅲ),La(NO)3×6H2O,与二乙醇胺(10.5g,0.1mol)一起加到反应混合物中。加入48%的氢氧化钠溶液调反应混合物的pH至11。反应混合物于85℃及回流冷凝器下搅拌10小时。冷却反应混合物,用浓硫酸进行酸化(pH1.8)。此后,将反应混合物再次加热到60℃,加入10g草酸和50ml水,反应混合物于60℃下搅拌20分钟,过滤热溶液除去形成的沉淀。滤液冷却,过滤除去随后形成的任何沉淀。从剩余的溶液中(42ml)(其含有54%的水),采用13CNMR光谱和质谱,分析出有机化合物为甲硅烷基或甲基酯衍生物。
从13C NMR光谱中鉴别出BCEEAA和BCEEA。在对照光谱的基础上,鉴别出未反应的起始物质:二乙醇胺和马来酸。作为反应的副产物,形成了苹果酸和富马酸;这些都可在对照光谱的基础上鉴别出来。
在定量13C NMR光谱分析的基础上,得到了反应产物中有机化合物的组成:
%重量BCEEAA 13.8BCEEA 4.5二乙醇胺 7.5马来酸, 2.3苹果酸 1.3富马酸 0.3
Claims (13)
2、权利要求1中的化合物,其特征在于式(Ⅰ)化合物为N-双-[(1,2-二羧基-乙氧基)乙基]胺或其Na+,K+,Ca2+,或Mg2+盐。
3、权利要求1中的化合物,其特征在于化合物为N-双-[(1,2-二羧基-乙氧基)乙基]天冬氨酸或其Na+,K+,Ca2+,或Mg2+盐。
4、权利要求1中的化合物,其特征在于化合物为N-三-[(1,2-二羧基-乙氧基)乙基]胺或其Na+,K+,Ca2+,或Mg2+盐。
5、制备权利要求1的式(Ⅰ)化合物的方法,其特征在于采用镧化物,镧化物或碱土金属化合物的混合物作为催化剂使二或三乙醇胺与马来酸的碱金属或碱土金属盐进行反应,形成式Ⅰ化合物。
6、权利要求5中的方法,其特征在于在La3+-催化剂的存在下,使二或三乙醇胺与马来酸的碱金属或碱土金属盐进行反应,形成式Ⅰ化合物。
7、权利要求5中的方法,其特征在于使马来酸酐与碱金属或碱土金属的氢氧化物或碳酸盐进行反应,来制备马来酸的碱金属或碱土金属盐。
8、权利要求5中的方法,其特征在于反应在75-95℃下进行。
9、式Ⅰ化合物作为金属螯合剂的用途。
10、式Ⅰ化合物作为金属螯合剂在浆状物漂白方面的用途。
11、式Ⅰ化合物在含有过氧化氢或过氧化物的碱性水溶液中的用途。
12、式Ⅰ化合物作为螯合剂在洗涤剂,清洗剂和消毒剂方面的用途。
13、式Ⅰ化合物作为螯合剂在摄影化学方面的用途。
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FI962261A FI112075B (fi) | 1996-05-30 | 1996-05-30 | N-bis- tai N-tris-[(1,2-dikarboksyyli-etoksi)-etyyli]amiinijohdannaiset, niiden valmistus ja käyttö |
FI962261 | 1996-05-30 |
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CN1220659A true CN1220659A (zh) | 1999-06-23 |
CN1158243C CN1158243C (zh) | 2004-07-21 |
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US (1) | US6093849A (zh) |
EP (1) | EP0904263B1 (zh) |
JP (1) | JP3901735B2 (zh) |
CN (1) | CN1158243C (zh) |
AT (1) | ATE198316T1 (zh) |
AU (1) | AU2964397A (zh) |
BR (1) | BR9709393A (zh) |
CA (1) | CA2256559C (zh) |
DE (1) | DE69703796T2 (zh) |
ES (1) | ES2154902T3 (zh) |
FI (1) | FI112075B (zh) |
PT (1) | PT904263E (zh) |
WO (1) | WO1997045396A1 (zh) |
Cited By (4)
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CN102933297A (zh) * | 2010-06-02 | 2013-02-13 | 凯米罗总公司 | 催化剂的回收方法 |
CN102933544A (zh) * | 2010-06-02 | 2013-02-13 | 凯米罗总公司 | 螯合剂混合物的制备方法 |
CN106062273A (zh) * | 2014-01-30 | 2016-10-26 | 昂高法国有限公司 | 含被碳酸盐和羧酸配体配合的多价金属的水性组合物及其用途 |
CN110959001A (zh) * | 2017-06-30 | 2020-04-03 | 凯米拉公司 | 制备螯合剂混合物的方法、螯合剂混合物及其使用方法 |
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FI105214B (fi) * | 1997-11-13 | 2000-06-30 | Kemira Chemicals Oy | Tehostettu kemiallisen massan valkaisumenetelmä |
FI106258B (fi) | 1998-03-09 | 2000-12-29 | Kemira Chemicals Oy | Menetelmiä N-bis-[2-(1,2-dikarboksi-etoksi)-etyyli]amiinijohdannaisen valmistamiseksi sekä menetelmien tuotteet ja niiden käytöt |
JP4632500B2 (ja) * | 1999-09-03 | 2011-02-16 | 株式会社日本触媒 | アミノ酸誘導体組成物及びアミノ酸誘導体の製造方法 |
EP1086944B1 (en) * | 1999-09-03 | 2005-05-25 | Nippon Shokubai Co., Ltd. | Amino acid derivative composition and process for producing an amino acid derivative |
US9745504B2 (en) | 2013-03-21 | 2017-08-29 | Halliburton Energy Services, Inc. | Wellbore servicing compositions and methods of making and using same |
US9512348B2 (en) | 2013-03-28 | 2016-12-06 | Halliburton Energy Services, Inc. | Removal of inorganic deposition from high temperature formations with non-corrosive acidic pH fluids |
CN106905171B (zh) * | 2017-03-31 | 2018-12-11 | 浙江大学 | 2-[2-叔丁氧基乙氧基]-乙胺的制备方法 |
BR112019027836A2 (pt) | 2017-06-30 | 2020-07-07 | Kemira Oyj | processo para preparação de mistura de agentes quelantes, mistura de agentes quelantes e métodos de uso dos mesmos |
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US4044034A (en) * | 1975-07-22 | 1977-08-23 | The Miranol Chemical Company, Inc. | Nitrogenous condensation products |
JP2896541B2 (ja) * | 1991-09-11 | 1999-05-31 | コニカ株式会社 | ハロゲン化銀写真感光材料用処理液 |
JPH06282044A (ja) * | 1993-03-26 | 1994-10-07 | Konica Corp | ハロゲン化銀写真感光材料用固形処理剤包装体 |
JPH07120894A (ja) * | 1993-10-21 | 1995-05-12 | Fuji Photo Film Co Ltd | 写真用処理組成物及び処理方法 |
JPH07120899A (ja) * | 1993-10-27 | 1995-05-12 | Fuji Photo Film Co Ltd | 写真用処理組成物及び処理方法 |
JPH07261355A (ja) * | 1994-03-17 | 1995-10-13 | Fuji Photo Film Co Ltd | カラー写真用処理装置および処理方法 |
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Cited By (8)
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CN102933297A (zh) * | 2010-06-02 | 2013-02-13 | 凯米罗总公司 | 催化剂的回收方法 |
CN102933544A (zh) * | 2010-06-02 | 2013-02-13 | 凯米罗总公司 | 螯合剂混合物的制备方法 |
CN102933544B (zh) * | 2010-06-02 | 2014-09-17 | 凯米罗总公司 | 螯合剂混合物的制备方法 |
CN102933297B (zh) * | 2010-06-02 | 2015-04-15 | 凯米罗总公司 | 催化剂的回收方法 |
CN106062273A (zh) * | 2014-01-30 | 2016-10-26 | 昂高法国有限公司 | 含被碳酸盐和羧酸配体配合的多价金属的水性组合物及其用途 |
CN106062273B (zh) * | 2014-01-30 | 2019-11-12 | 昂高法国有限公司 | 含被碳酸盐和羧酸配体配合的多价金属的水性组合物及其用途 |
CN110959001A (zh) * | 2017-06-30 | 2020-04-03 | 凯米拉公司 | 制备螯合剂混合物的方法、螯合剂混合物及其使用方法 |
CN110959001B (zh) * | 2017-06-30 | 2022-09-20 | 凯米拉公司 | 制备螯合剂混合物的方法、螯合剂混合物及其使用方法 |
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Publication number | Publication date |
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ATE198316T1 (de) | 2001-01-15 |
EP0904263A1 (en) | 1999-03-31 |
AU2964397A (en) | 1998-01-05 |
US6093849A (en) | 2000-07-25 |
DE69703796T2 (de) | 2001-04-19 |
PT904263E (pt) | 2001-04-30 |
ES2154902T3 (es) | 2001-04-16 |
JP2000515121A (ja) | 2000-11-14 |
DE69703796D1 (de) | 2001-02-01 |
WO1997045396A1 (en) | 1997-12-04 |
CN1158243C (zh) | 2004-07-21 |
EP0904263B1 (en) | 2000-12-27 |
JP3901735B2 (ja) | 2007-04-04 |
FI962261A (fi) | 1997-12-01 |
FI962261A0 (fi) | 1996-05-30 |
BR9709393A (pt) | 1999-08-10 |
CA2256559A1 (en) | 1997-12-04 |
CA2256559C (en) | 2006-05-02 |
FI112075B (fi) | 2003-10-31 |
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