CN1344313A - Process for forming agglomerated particle - Google Patents
Process for forming agglomerated particle Download PDFInfo
- Publication number
- CN1344313A CN1344313A CN98814325.9A CN98814325A CN1344313A CN 1344313 A CN1344313 A CN 1344313A CN 98814325 A CN98814325 A CN 98814325A CN 1344313 A CN1344313 A CN 1344313A
- Authority
- CN
- China
- Prior art keywords
- acid
- unit
- sensitive
- mixture
- 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
Links
- 239000002245 particle Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 86
- 230000008569 process Effects 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 180
- 239000000463 material Substances 0.000 claims abstract description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 84
- 238000002156 mixing Methods 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 72
- 230000000694 effects Effects 0.000 claims description 69
- 229920000642 polymer Polymers 0.000 claims description 62
- 239000000126 substance Substances 0.000 claims description 56
- 229920000768 polyamine Polymers 0.000 claims description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 39
- 230000004048 modification Effects 0.000 claims description 37
- 238000012986 modification Methods 0.000 claims description 37
- 238000005054 agglomeration Methods 0.000 claims description 33
- 230000002776 aggregation Effects 0.000 claims description 33
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000002431 hydrogen Chemical group 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical group 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 4
- 239000011162 core material Substances 0.000 abstract 4
- 229920002873 Polyethylenimine Polymers 0.000 description 48
- 238000004140 cleaning Methods 0.000 description 14
- 150000003141 primary amines Chemical class 0.000 description 14
- 239000013543 active substance Substances 0.000 description 12
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 12
- 239000003945 anionic surfactant Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 150000003335 secondary amines Chemical class 0.000 description 9
- 150000003512 tertiary amines Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 5
- 150000004646 arylidenes Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 235000014347 soups Nutrition 0.000 description 5
- 241000234282 Allium Species 0.000 description 4
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 4
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 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 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000001204 N-oxides Chemical class 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- PODAMDNJNMAKAZ-UHFFFAOYSA-N penta-2,3-diene Chemical group CC=C=CC PODAMDNJNMAKAZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- QCYOIFVBYZNUNW-UHFFFAOYSA-N 2-(dimethylazaniumyl)propanoate Chemical compound CN(C)C(C)C(O)=O QCYOIFVBYZNUNW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JLPQBGFDPOFXJA-UHFFFAOYSA-N CCCCCCCCC([O])=O Chemical compound CCCCCCCCC([O])=O JLPQBGFDPOFXJA-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZUBJEHHGZYTRPH-KTKRTIGZSA-N [(z)-octadec-9-enyl] hydrogen sulfate Chemical compound CCCCCCCC\C=C/CCCCCCCCOS(O)(=O)=O ZUBJEHHGZYTRPH-KTKRTIGZSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000006841 cyclic skeleton Chemical group 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- GSPKZYJPUDYKPI-UHFFFAOYSA-N diethoxy sulfate Chemical compound CCOOS(=O)(=O)OOCC GSPKZYJPUDYKPI-UHFFFAOYSA-N 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical class [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000009827 uniform distribution Methods 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
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Abstract
The present invention relates to a process for forming an agglomerated particle containing the steps of providing at least one alkaline material, a core material, and at least one acid active. The alkaline material and the core material are added to a mixer and agglomerated therein, to form an agglomerated particle comprising an interior and an exterior. The acid active is then added to the mixer. The core material is concentrated into the interior of the agglomerated particle by adding substantially of the core material to the alkaline material before more than about 50% of the acid active is added to mixer.
Description
The present invention relates to form the method for agglomerated particle, specifically, the present invention relates to form the method for the agglomerated particle that contains polymkeric substance.
Background
Agglomerated particle in cleaning composition, the especially agglomerated particle in laundry composition will contain the acidic substance that exist in process of production usually.For example, production process can be used the acid activity form of anion surfactant, and it is neutralized in process of production.And the tensio-active agent that some anion surfactant can be used as pre-neutralization in some occasion adds, the tensio-active agent of this pre-neutralization can be unavailable, and quality is insecure or undue costliness, therefore, typical production process adds the acid activity material, therein with its neutralization.
Some material, for example polymkeric substance adds in the agglomerated particle usually so that soil dispersion character, antiredeposition character, fabric-conditioning character etc. to be provided.In addition, some high-melting-point liquid comprises that some polymkeric substance, tensio-active agent soup compound, suds booster etc. also can add in the agglomerated particle so that additional required character to be provided, and for example washs character, brightens character, foam levels adjusting etc.And the kind of polymkeric substance and high-melting-point polymer is overlapping, does not have one group to be other complete subgroup.Therefore, any or their combination can be present in the agglomerated particle.One type the polymkeric substance that is particularly useful for agglomerated particle is a modified polyamine polymers, and this modified polyamine polymers provides one or more required as discussed above character usually.Specifically, this modified polyamine polymers can for example provide soil dispersion, antiredeposition and the fabric-conditioning character of improvement, and the polyamine polymer of modification can contain and for example is connected in the additional charged of polymer backbone or charged group not.
Agglomeration process produces agglomerated particle, and it contains many concentric layers, is similar to onion.Common polymkeric substance can add in the agglomeration process or when agglomeration process finishes with the acid activity material and add with liquid vehicle.These methods obtain the uniform distribution of polymkeric substance in the different layers of whole " onion " respectively, or polymkeric substance is concentrated in the extexine of " onion ".
The required character of these polymkeric substance depends on the character of their molecular weight and coupled any modification group usually.Above-mentioned character is normally with concentration dependent, and the concentration of polymkeric substance is big more, and effect is big more.Yet, this polymkeric substance, especially modified polyamine polymers, it produces normally expensive.Therefore, they use with quite low concentration usually.Therefore, need to add the polymkeric substance of effective concentration, also keep the sufficiently low formulation cost of this concentration with increase cleaning composition within reason.
The particle cleaning composition that contains high-melting-point liquid lumps or agglomeration in storage process usually easily, and no matter from the still reason of performance attractive in appearance, the particle of this caking is undesirable.For example compare with free flowing granule, agglomerated grain needs the long time to dissolve usually.Dissolving or incomplete dissolved particle also can not left over unwanted film or remnants on the dirt-carrying body.
Therefore, people still need a kind of polymkeric substance is not increased formulation cost to keep polymer property, unrestricted flow character and performance profile concentration to add the method for agglomerated particle, also need high-melting-point liquid added agglomerated particle and keep the method for acceptable unrestricted flow character simultaneously.
General introduction
We find now the acid activity material that exists some polymkeric substance of can degrading in agglomeration process, cause them to be decomposed into the fragment of lower molecular weight, and they are providing obviously not too effective aspect the required polymer property.Therefore this polymkeric substance is called " acid-sensitive sensitive polymeric " in this article.In addition, we find that now high-melting-point liquid can add in the agglomerated particle and keeps acceptable unrestricted flow character simultaneously.Therefore, the present invention relates to a kind of improvement method that forms agglomerated particle, described agglomerated particle contains the acid activity material and is selected from the core substance of acid-sensitive sensitive polymeric, high-melting-point liquid and their mixture.When having acid-sensitive sensitive polymeric, the method for this improvement is by the inner degraded that reduces acid-sensitive sensitive polymeric of the alkalescence that it is concentrated into agglomerated particle, the polymer property that is maintained, unrestricted flow character and performance profile and do not increase formulation cost.When high-melting-point liquid was used for herein, the method for improvement was by being concentrated to it inner unrestricted flow character that keeps agglomerated particle of particulate.
The present invention relates to form the method for agglomerated particle, it contains provides at least a alkaline matter, be selected from acid-sensitive sensitive polymeric, high-melting-point liquid and the core substance of their mixture and the step of at least a acid activity material.Alkaline matter and core substance add in the mixing tank, and agglomeration therein contains inside and outside agglomerated particle with formation, add the acid activity material subsequently in mixing tank.In core substance adding alkaline matter that will be all basically before the acid activity material that surpasses about 50% adds mixing tank, core substance is concentrated to the inside of agglomerated particle.
By reading disclosure and appending claims, those skilled in the art will know these and other feature of the present invention, aspect and advantage.
Describe in detail
According to the present invention, we find that agglomerated particle can use acid activity material and acid-sensitive sensitive polymeric simultaneously, the degraded of also having avoided the acid in time of acid-sensitive sensitive polymeric to cause.The method of improving has reduced degraded, thereby has improved the validity of a certain amount of acid-sensitive sensitive polymeric in the cleaning composition.Owing to do not need to add the degraded of extra acid-sensitive sensitive polymeric with the compensation expection, the method for improvement can also keep polymer properties profile and benefit and reduce formulation cost simultaneously.When high-melting-point liquid was used for this paper, present method had also obtained having acceptable unrestricted flow character, for example agglomerated particle of the caking of Jiang Diing.
All percentage ratios, ratio and ratio are by agglomerated particle weight, except as otherwise noted.All temperature be degree centigrade (℃), except as otherwise noted.The document of all references is listed this paper in as a reference.
The term " alkyl " that is used for this paper is meant straight or branched, saturated or undersaturated alkyl; except as otherwise noted; alkyl preferably saturated or two keys undersaturated, preferably have one or two pair key, being included in the term " alkyl " is the moieties of acyl group.
The revolution that is used for term " RPM " the expression per minute of this paper.
According to the present invention, we recognize and some material that for example high-melting-point liquid, the acid-sensitive sensitive polymeric specific question relevant with their mixture can be avoided by the core that they is added agglomerated particle, and this material is called " core substance " hereinafter.According to the present invention, we recognize acid, the acid activity material that in common agglomeration process, exists some polymkeric substance of can degrading especially, thus reduce their effects in cleaning composition.Therefore, this polymkeric substance is referred to herein as " acid-sensitive sensitive polymeric ".Although do not plan to be limited to theory, we believe that the acid activity material can react to cause its degraded with acid-sensitive sensitive polymeric, for example reacts to reduce the character of acid-sensitive sensitive polymeric in cleaning composition, for example soil dispersion character with active group.In addition, the acid activity material can with the reaction of acid-sensitive sensitive polymeric skeleton, with its hydrolysis with resolve into less fragment, they are obviously not too effective in cleaning composition.
Method of the present invention has also reduced the unwanted polymerization of acid-sensitive sensitive polymeric.Although do not plan to be limited to theory, but we believe that some acid-sensitive sensitive polymeric can not form homopolymer or multipolymer with catering to the need when being exposed to acid, and polymkeric substance effect and the performance in the final composition can be destroyed or be reduced in to this undesirable polymerization process.
Though at common detergent composition neutral and alkali material is excessive, we were surprised to find after agglomeration process is finished several hours, and (for example about 20-50%) may not exclusively neutralize at quite most acid activity material.Therefore, we find can need several days with the neutralization fully that becomes at the acid activity material that the agglomerated particle outside exists, or in some cases, never neutralization fully.Therefore, we recognize when the acid activity material that exists is neutralized at once that it is acid that the acid activity material that exists still keeps for a long time after agglomeration process is finished in the particulate outside in the inside of agglomerated particle.In this process, if acid-sensitive sensitive polymeric is dispersed in the whole particle, the acid activity material that exists in the outside of agglomerated particle these acid-sensitive sensitive polymerics of can degrading.
In agglomeration process, at first the component of Jia Ruing is concentrated to particulate inside usually, subsequently the component of Jia Ruing appear at that particulate is concentric, in the skin successively.Method of the present invention is before the acid activity material that surpasses 50% adds mixing tank, and all core substances add in the alkaline matter basically.After core substance adds in the mixing tank, add remaining acid activity material, after agglomeration process proceeds to all components adding.
When core substance contained acid-sensitive sensitive polymeric, the method for this improvement was by being concentrated to acid-sensitive sensitive polymeric the very alkaline inside of agglomerated particle, and promptly the inside of " onion " has reduced degraded.Although do not plan to be limited to theory, we believe that the inside of agglomerated particle provides alkaline environment, and it prevents acid-sensitive sensitive polymeric because the degraded that acid causes.In addition, we believe since acid-sensitive sensitive polymeric everywhere by the excesses of basic substances encircle, DeR drops to minimum; Therefore, any acid activity material that exists with acid-sensitive sensitive polymeric, it have an opportunity with acid-sensitive sensitive polymeric reaction before, with excessive alkali substance reaction, be neutralized basically immediately.
In addition, method of the present invention protects acid-sensitive sensitive polymeric to avoid remaining in the acid activity material of agglomerated particle outside.In the agglomerated particle of the inventive method preparation, the inside of containing acid-sensitive sensitive polymeric is surrounded by many layer alkaline matter layers, and the layer of these encirclements also protects acid-sensitive sensitive polymeric to avoid the degraded of acid activity material.Therefore, because acid-sensitive sensitive polymeric is concentrated in particulate inside, the middle layer that any acid activity material that remains in the particle outside must be by many alkaline matters is reaching, and then the degradation acid sensitive polymer.Because outside acid activity material was neutralized before arriving acid-sensitive sensitive polymeric equally, the embracing layer of alkaline matter provides the extra play of protection.
The method of improving also provides additional effect.For example, because acid-sensitive sensitive polymeric is normally expensive, the present invention adds less acid-sensitive sensitive polymeric by needs and has reduced formulation cost so that identical beneficial effect to be provided.On the contrary, because effective effect of this acid-sensitive sensitive polymeric depends on their concentration in cleaning composition usually, method of the present invention has been improved the general effect of certain density acid-sensitive sensitive polymeric.
When core substance contained high-melting-point liquid, method of the present invention also provided the surprised advantage of producing the free flowing powder of the caking susceptibility with reduction.This feature is very to need in the particle cleaning composition, because it has improved the attractive in appearance and solubility curve of composition.Although do not plan to be limited to any theory, we believe that it is distributed in the whole particle when high-melting-point liquid adds in the typical agglomeration process, yet in this particle, high-melting-point liquid can for example be diffused into the particulate surface in time in storage process.When this thing happens, the particle thickness that becomes itself trended towards and other particle caking, and this further produces caking, has reduced the unrestricted flow character of composition, thereby caused the performance and the solvability that reduce.Yet we are surprised to find when this high-melting-point liquid is concentrated in the inside of agglomerated particle by method of the present invention now, keep acceptable unrestricted flow character.Although do not plan to be limited to theory, but we believe when it is concentrated in the inside of agglomerated particle rather than is dispersed in the whole particle, the less surface that is diffused into of high-melting-point liquid, and this generation has the particle of acceptable unrestricted flow character, it is not too sticking, not too trends towards caking and reunion.In addition, when high-melting-point liquid when still being acid-sensitive sensitive polymeric, this method has reduced the degraded of sour initiation by the outside that reduces acid-sensitive sensitive polymeric and be diffused into agglomerated particle.Agglomerated particle itself by method preparation of the present invention can be used as cleaning composition, or can mix with other component to form cleaning composition.
In the method for the invention, provide at least a alkaline matter, its neutralizing acid active substance.Alkaline matter can be the material of any cleaning composition that is used for, especially laundry composition.Alkaline matter is selected from basic metal and alkaline earth metal carbonate, phosphoric acid salt, silicate, layered silicate, oxyhydroxide and their mixture usually.
The preferred embodiment that is used for the carbonate of this paper comprises supercarbonate and sesquicarbonate, more preferably yellow soda ash (being SODA ASH LIGHT 99.2), salt of wormwood and their mixture.
If allow, basic metal and alkali earth metal phosphate are particularly useful for this paper, because they can be used as alkaline matter and washing assistant simultaneously.If exist, washing assistant will help to control hardness of minerals and remove dirt particles.The preferably phosphate that is used for this paper includes, but not limited to polyphosphate (for example tri-polyphosphate, pyrophosphate salt and vitreous state polymer metaphosphate), basic metal, ammonium and the alkanol ammonium salts of phosphonate and their mixture.
Basic metal and alkaline earth metal silicate and layered silicate also are applicable to this paper.The example of silicate-like builder is an alkalimetal silicate, particularly those SiO
2: Na
2The O ratio is 1.6: 1-3.2: 1 silicate and layered silicate, and as the lamina sodium silicate of in the US4664839 of the Rieck of on May 12nd, 1987 promulgation, describing.NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " usually at this) by the crystalline layered silicate of Hoechst sale.NaSKS-6 has the δ-Na of layered silicate
2SiO
5Form, SKS-6 a kind ofly is used for preferred layered silicate of the present invention, but also can use other this class layered silicate, as has general formula NaMSi
xO
2x+1YH
2The silicate of O, wherein M is sodium or hydrogen, x is the number between the 1.9-4, is preferably 2, and y is the number between the 0-20, is preferably 0.Other various layered silicates from Hoechst comprise NaSKS-5, NaSKS-7 and the NaSKS-11 that is respectively α, β and γ form.As mentioned above, δ-Na
2SiO
5(NaSKS-6 form) be most preferably be used for of the present invention.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be used as crisp dose in granular recipe, as the stablizer of oxygen bleaching agent, and as the component in the foam control system.
The oxyhydroxide that is used for this paper is sodium hydroxide preferably, for example is used for the causticity neutralization method.Usually the aqueous solution with caustic sodium hydroxide adds in the mixing tank with the neutralizing acid active substance.
The alkaline matter that is used for this paper is present in cleaning composition with the stoichiometric mol ratio that is enough to complete neutralizing acid active substance at least usually, and alkaline matter is that stoichiometry is excessive usually.The stoichiometry mol ratio of alkaline matter and acid activity material is at least 1: 1, preferably at least about 4: 1, more preferably at least about 7: 1.
Core substance provided herein is selected from acid-sensitive sensitive polymeric, high-melting-point liquid and their mixture.When some acid-sensitive sensitive polymeric was high-melting-point liquid equally, these classification also comprised many non-overlapped compounds, therefore, followingly went through both.
Acid-sensitive sensitive polymeric provided herein is undesirably degraded when being exposed to the acid activity material.As mentioned above, this degradation process can be for example produced, is produced or produced by unwanted polymerization process by the actual division of the skeleton of acid-sensitive sensitive polymeric by the chemical reaction with the active group of acid-sensitive sensitive polymeric.The preferred acid sensitive polymer that is used for this paper comprises soil dispersion polymkeric substance, antiredeposition polymkeric substance, fabric-conditioning polymkeric substance and their mixture.The more preferably kind that is used for the polymkeric substance of this paper comprises modified polyamine polymers, polyacrylate polymers, vinylformic acid and maleic acid and their mixture.
Modified polyamine polymers is especially preferred as acid-sensitive sensitive polymeric, and these polymkeric substance are adding the degraded susceptibility that the high acid of fashionable demonstration causes with the acid activity material in the agglomeration process usually.The modified polyamine polymers that is used for this paper is more preferably the modified polyethyleneimine polymers that contains straight chain or cyclic skeleton.Polyamine backbone can also contain the polyamine side chain of bigger or less degree.Usually, polyamine backbone described herein modification as follows makes that each nitrogen of polyamine chain is described to replace, quaternized, oxidation or their bonded unit.
Being used for hydrogen atom (replacement), quaternized skeleton nitrogen (quaternized) or oxidation skeleton nitrogen that term of the present invention " modification " is defined as replacing with the E unit skeleton-NH is N-oxide compound (oxidation).Replace when being connected in the hydrogen atom of skeleton nitrogen when relating to the E unit, term " modification " and " replacement " are used interchangeably.Quaternized or oxidation can be carried out under some occasion that does not have to replace, but replaces preferred oxidation or quaternized finishing by at least one skeleton nitrogen.
The straight chain or the non-annularity polyamine backbone that comprise modified polyethyleneimine polymers of the present invention have following general formula:
Described skeleton before modification subsequently, contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen.The cyclic polyamines skeleton that modified polyethyleneimine polymers of the present invention contained has following general formula:
Described skeleton before modification subsequently, contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen.
Be used for of the present inventionly comprising the skeleton of modification or the primary amine nitrogen of side chain is defined as V or Z " end " unit.For example, when the primary amine part with following structure that is positioned at a main polyamine backbone or a link ends is carried out modification according to the present invention:
H
2N-R]-
It is defined as V " end " unit subsequently, or abbreviates the V unit as.Yet, in the present invention, be subjected to the following restriction that further describes, partly or entirely the primary amine part can keep unmodified.Consider its position in skeletal chain, these unmodified primary amine parts still are " end " unit.Equally, when the primary amine part with following structure that is positioned at main polyamine backbone end is carried out modification according to the present invention:
-NH
2
It is defined as Z " end " unit subsequently, or abbreviates the Z unit as.Yet, in the present invention, being subjected to the following restriction that further describes, it is unmodified that this unit can keep.
Equally, comprise the skeleton of modification or the secondary amine nitrogen of side chain and be defined as W " skeleton " unit.For example, when secondary amine part, when the major portion of skeleton of the present invention or side chain is carried out modification according to the present invention with following structure:
It is defined as W " skeleton " unit subsequently, or abbreviates the W unit as.Yet in the present invention, partly or entirely the secondary amine part can keep unmodified.Consider its position in skeletal chain, these unmodified secondary amine parts still are " skeleton " unit.
Equally, the tertiary amine nitrogen that skeleton or side chain contained that comprises modification further is called Y " side chain " unit.For example, when having following structure, be the tertiary amine part of the chain fulcrum of polyamine backbone or other side chain or ring when carrying out modification according to the present invention:
Wherein B represents the continuity by the chain structure of side chain, and it is defined as Y " side chain " unit subsequently, or abbreviates the Y unit as.Yet in the present invention, partly or entirely the tertiary amine part can keep unmodified.Consider its position in skeletal chain, these unmodified tertiary amine parts still are " side chain " unit.The R unit that following description and the V that is used to be connected polyamine nitrogen, W are connected with Y unit nitrogen.
The final modified structure of modified polyethyleneimine polymers of the present invention can be represented with following general formula for the straight chain modified polyethyleneimine polymers:
V
(n+1)W
mY
nZ
Can represent with following general formula for the ring-type modified polyethyleneimine polymers:
V
(n-k+1)W
mY
nY’
kZ
Containing under the modified polyethyleneimine polymers situation of ring the Y ' unit of following formula:
Side chain point as a skeleton or a chain link.For each Y ' unit, there is the Y unit of following formula:
It will form the tie point of ring and host polymer chain or side chain.Skeleton is that polyamine backbone has following formula under the single situation of encircling completely therein:
Thereby do not contain the Z terminal units, and have following formula:
V
n-kW
mY
nY’
k
Wherein k is the quantity that forms the unitary ring of side chain.Polyamine backbone of the present invention does not preferably contain ring.
Under the situation of acyclic modified polyethyleneimine polymers, the ratio of coefficient n and Coefficient m is called the side chain relative extent.Complete non-side chain straight chain modified polyethyleneimine polymers of the present invention has following formula:
VW
mZ
Be that n equals 0.N value big more (ratio of m and n is more little), the side chain degree is big more in the molecule.The scope of m value is about 400 from minimum value 4-usually, yet bigger m value also is preferred, especially in the value of coefficient n very little or near 0 in.
Each polyamine nitrogen, no matter it be primary, the second month in a season or uncle's nitrogen, in case carry out modification, also be defined as a kind of in three kinds of common kinds: simply replace, quaternized or oxidation according to the present invention.Those unmodified polyamine nitrogen unit according to its be primary, the second month in a season or uncle's nitrogen, be categorized as V, W, Y or Z unit.Be that unmodified primary amine nitrogen among the present invention is V or Z unit, unmodified secondary amine nitrogen is that W unit and unmodified tertiary amine nitrogen are the Y unit.
The modification primary amine partly is defined as V " end " unit with one of following three kinds of forms:
A) have the simple replacement unit of following structure:
B) have the quaternized unit of following structure:
Wherein X provides the suitable counter ion of charge balance; With
C) have the oxidation unit of following structure:
Modification secondary amine partly is defined as W " skeleton " unit with one of following three kinds of forms:
A) have the simple replacement unit of following structure:
B) have the quaternized unit of following structure:
Wherein X provides the suitable counter ion of charge balance; With
C) have the oxidation unit of following structure:
Enhanced tertiary amine partly is defined as Y " side chain " unit with one of following three kinds of forms:
A) have the unmodified unit of following structure:
B) have the quaternized unit of following structure:
Wherein X provides the suitable counter ion of charge balance; With
C) have the oxidation unit of following structure:
Some modification primary amine partly is defined as Z " end " unit with one of following three kinds of forms:
A) have the simple replacement unit of following structure:
B) have the quaternized unit of following structure:
Wherein X provides the suitable counter ion of charge balance; With
C) have the oxidation unit of following structure:
When the position on any nitrogen is unmodified the replacement, be appreciated that hydrogen will replace E.The unitary primary amine of the E unit that for example contains a hydroxyethyl portion-form is the V terminal units with following formula:
(HOCH
2CH
2)HN-。
There is two types chain end unit in the present invention, V and Z unit.Z " end " unit is by structure-NH
2The terminal primary amine moiety obtain, non-annularity polyamine backbone of the present invention only comprises a Z unit, thus cyclic polyamines can not comprise the Z unit.Except when outside the Z unit was modified when forming the N-oxide compound, Z " end " unit can replace with any E as described below unit.Z unit nitrogen is oxidized under the situation of N-oxide compound therein, and nitrogen must be modified, thereby E can not be a hydrogen.
Modified polyethyleneimine polymers of the present invention comprises skeleton R " connection " unit, and it is used to connect the nitrogen-atoms of skeleton.Contain and be useful on unitary R of the present invention unit and be called " alkyl R " unit and " oxygen base R " unit." alkyl " R unit is C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene, wherein except the carbon atom that is directly connected in polyamine backbone nitrogen, any position, C that hydroxylic moiety can be on the R cellular chain
4-C
12Alkyl sub-dihydroxy, wherein except the carbon atom that is directly connected in polyamine backbone nitrogen, hydroxylic moiety can connect any two carbon atoms, the C on the R cellular chain
8-C
12The dialkyl group arylidene, it is the arylidene part that contains as two alkyl substituents of connection chain part in the present invention.For example, the dialkyl group arylidene that has following formula:
Though the unit needs not to be 1,4-replaces, and also can be 1,2 or 1,3 C that replaces
2-C
12Alkylidene group, preferred ethylidene, propylene and their mixture, most preferably ethylidene." oxygen base " R unit comprises-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-CH
2CH (OR
2) CH
2-,-(R
1O)
xR
1-and their mixture.The R unit is C preferably
2-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(R
1O)
xR
1-,-CH
2CH (OR
2) CH
2-,-(CH
2CH (OH) CH
2O)
z(R
1O)
yR
1(OCH
2CH-(OH) CH
2)
w-,-(R
1O)
xR
5(OR
1)
x-; The R unit is more preferably C
2-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OH) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OH) CH
2)
w-and their mixture; The R unit is C preferably also
2-C
12Alkylidene group, C
3Hydroxy alkylidene and their mixture; C most preferably
2-C
6Alkylidene group.Most preferred skeleton of the present invention contain at least 50% be the R unit of ethylidene.
R
1The unit is C
2-C
6Alkylidene group and their mixture, preferred ethylidene; R
2Be hydrogen and-(R
1O)
xB, preferred hydrogen.
R
3Be C
1-C
18Alkyl, C
7-C
12Aryl alkylene, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl and their mixture, preferred C
1-C
12Alkyl, C
7-C
12Aryl alkylene, more preferably C
1-C
12Alkyl, most preferable.R
3The unit is as the unitary part of E described below.
R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene, preferred C
1-C
12Alkylidene group and C
8-C
12Aryl alkylene, more preferably C
2-C
8Alkylidene group, most preferably ethylidene or butylidene.
R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-C (O) (R
4)
rC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-, R
5Preferably ethylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH-(OH) CH
2-, be more preferably-CH
2CH (OH) CH
2-.
R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene.
Preferably " oxygen base " R unit is at R
1, R
2And R
5Further definition in the unit.Preferably " oxygen base " R unit comprises preferred R
1, R
2And R
5The unit.Preferred modified polyethyleneimine polymers of the present invention contains at least 50% and is the R of ethylidene
1The unit.Preferred R
1, R
2And R
5The unit combines with " oxygen base " R unit and obtains following preferred " oxygen base " R unit.
I) at-(CH
2CH
2O)
xR
5(OCH
2CH
2)
x-replace preferred R
5Obtain-(CH
2CH
2O)
xCH
2CHOHCH
2(OCH
2CH
2)
x-.
Ii) at-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1O (CH
2CH (OR
2) CH
2)
wThe preferred R of-middle replacement
1And R
2Obtain-(CH
2CH (OH) CH
2O)
z(CH
2CH
2O)
yCH
2CH
2O (CH
2CH (OH) CH
2)
w-.
Iii) at-CH
2CH (OR
2) CH
2The preferred R of-middle replacement
2Obtain-CH
2CH (OH) CH
2-.
The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Thiazolinyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
mB ,-C (O) R
3, preferred hydrogen, C
2-C
22Hydroxy alkylidene, benzyl, C
1-C
22Alkylidene group ,-(R
1O)
mB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M, more preferably C
1-C
22Alkylidene group ,-(R
1O)
xB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M, most preferably C
1-C
22Alkylidene group ,-(R
1O)
xB and-C (O) R
3When do not carry out modification or replacement on nitrogen, then hydrogen atom keeps the part represented as E.
Oxidized when V, W or Z unit, when promptly nitrogen was the N-oxide compound, the E unit did not contain hydrogen atom.For example skeletal chain or side chain do not comprise the unit of following structure:
In addition, oxidized when V, W or Z unit, when promptly nitrogen was the N-oxide compound, the E unit did not comprise the carbonyl that is directly connected in nitrogen-atoms.According to the present invention, E unit-C (O) R
3Part is not attached to the nitrogen of N-oxide modifying, does not promptly have the N-oxide compound acid amides with following structure:
Or their combination.
B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, preferred hydrogen ,-(CH
2)
qSO
3M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M, more preferably hydrogen or-(CH
2)
qSO
3M.
M is the water-soluble cationic that hydrogen or consumption are enough to satisfy charge balance.For example, sodium cation just in time satisfies-(CH
2)
pCO
2M and-(CH
2)
qSO
3M, thus obtain-(CH
2)
pCO
2Na and-(CH
2)
qSO
3The Na part.Can be in conjunction with to satisfy required chemical charge balance more than a kind of univalent cation (sodium, potassium etc.).Yet, surpass an anionic group and can use the divalent cation balancing charge, or need be more than one univalent cation to satisfy the electric charge needs of polyanionic group.For example with sodium atom replace-(CH
2)
pPO
3M partly has formula-(CH
2)
pPO
3Na
3Divalent cation, for example calcium (Ca
2+) or magnesium (Mg
2+) be used to replace or combine with other suitable unit price water-soluble cationic and be used for replacing, preferred cation is sodium and potassium, more preferably sodium.
X is a water soluble anion, for example chlorine (Cl
-), bromine (Br
-) and iodine (I
-) or X can be the group that has negative charge, sulfate radical (SO for example
4 2-) and methylsulfate (CH
3SO
3 -).
It is 1-6 that the general formula coefficient has following value: p, and q is 0-6; R is 0 or 1; W is 0 or 1; X is 1-100; Y is 0-100; Z is 0 or 1; M is 4-about 400; N is 0-about 200; M+n is at least 5.
Preferred modified polyethyleneimine polymers of the present invention contains and wherein is less than about 50% R group and comprises the unitary polyamine backbone of " oxygen base " R, preferably is less than approximately 20%, and more preferably less than 5%, most preferably the R unit does not comprise " oxygen base " R unit.
Not comprising the unitary most preferred modified polyethyleneimine polymers of " oxygen base " R contains and wherein is less than 50% R group and comprises the polyamine backbone that surpasses 3 carbon atoms.For example comprise 3 or still less ethylidene, propylene and the trimethylene of carbon atom are preferred " alkyl " R unit.Promptly working as skeleton R unit is C
2-C
12During alkylidene group, preferred C
2-C
3Alkylidene group, most preferably ethylidene.
Modified polyethyleneimine polymers of the present invention contains all even non-homogeneous polyamine backbone of modification, wherein 100% or less-NH unit be modified.Be used for term of the present invention " evenly polyamine backbone " and be defined as the polyamine backbone that contains identical R unit (for example whole ethylidene).Yet this identical definition is not got rid of and is contained the external unitary polyamine that other contains polymer backbone, and described polymer backbone is owing to the method for selected chemosynthesis exists.For example, those skilled in the art is known, thanomin is in polymine synthetic available " initiator ", and the polymine sample that contains a hydroxyethyl part that is produced by polymerization " initiator " will be considered to contain even polyamine backbone in the present invention.Comprising and wherein having the unitary polyamine backbone of unitary all the ethylidene R of non-side chain Y is even skeleton.Comprising the unitary polyamine backbone of all ethylidene R is and existing side chain degree or the irrelevant even skeleton of ring-type side chain number.
Be used for term of the present invention " non-homogeneous polymer backbone " and be meant polyamine backbone into the mixture of various R element lengths and R cell type.For example, non-homogeneous skeleton contains the R unit, and it is the unitary mixture of ethylidene and propylene." alkyl " and the unitary mixture of " oxygen base " R needn't provide non-homogeneous skeleton in the present invention.The suitable manipulation of these " R unit chain lengths " makes the water-soluble and fabric affinity that the makers-up can modification modified polyethyleneimine polymers of the present invention.
Preferred modified polyethyleneimine polymers of the present invention contains even polyamine backbone, it be all or part of by polyoxyethylene partly replace, all or part of quaternary ammonium, the nitrogen of all or part of N-of being oxidized to oxide compound and their mixture.Yet, the modification in the same manner of the nitrogen of not all skeleton amine, the special requirement that the makers-up is left in the modification selection for.Degree of ethoxylation is also determined by makers-up's special requirement.
The preferred polyamine normally polyalkenes amine (PAA), the polyalkenes imines (PAI) that contain the skeleton of The compounds of this invention, preferably polyethylene amine (PEA), polymine (PEI), or by having PEA or the PEI that the unitary part of the R longer than parent PAA, PAI, PEA or PEI connects.Usually polyalkenes amine (PAA) is four butylidenes, five amine.PEA by the reaction of ammonia and ethylene dichloride, obtains with aftercut usually.Usually the PEA that obtains is Triethylenetetramine (TETA) (TETA) and tetren (TEPA).Surpass five amine, i.e. hexylamine, heptyl amice, octylame and possible nonyl amine, the mixture that common kind obtains obviously can not pass through fractionation by distillation, can comprise other material, for example cyclammonium, especially piperazines.The cyclammonium that can also have the side chain of being with nitrogen atom.Referring to the US2792372 of the Dickinson that issues May 14 nineteen fifty-seven, it has described the preparation method of PEA.
Preferred amine polymer skeleton is included as C
2The unitary R of alkylidene group (ethylidene) unit also is called polymine (PEI).Preferred PEI contains medium at least side chain, and promptly the ratio of m and n is less than 4: 1, yet the ratio that most preferably has m and n is about 2: 1 PEI.Preferred skeleton has following general formula before modification:
Wherein the definition of m and n together as mentioned above.Preferred PEI has the about 200 daltonian molecular weight of surpassing before modification.
In polyamine backbone, especially under the situation of PEI, primary, the second month in a season and the unitary relative proportion of tertiary amine will change according to preparation method's mode.Each hydrogen atom that connects each nitrogen-atoms of polyamine backbone chain represents to be used for to replace subsequently, the potential site of quaternized or oxidation.
These modified polyethyleneimine polymers can be for example by at catalyzer, carbonic acid gas for example, polymerising ethylene imines preparation under the existence of sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc.The concrete grammar for preparing these polyamine backbone is disclosed in the US2553696 of the Wilson of the US2806839 of Crowther of US2208095, promulgation on September 17 nineteen fifty-seven of US3033746, the Esselmann of promulgation on July 16th, 1940 etc. of US2182306, the Mayle of promulgation on May 8th, 1962 etc. of the Ulrich of promulgation on December 5 nineteen thirty-nine etc. and promulgation on May 21 nineteen fifty-one, and they all classify this paper reference as.
The example that contains the modified polyethyleneimine polymers of the present invention of PEI illustrates with formula I-IV:
Formula I has narrated the modified polyethyleneimine polymers that contains the PEI skeleton, and wherein all commutable nitrogen are by using polyoxyethylene oxygen unit ,-(CH
2CH
2O)
7H replaces the hydrogen modification, and it has following formula:
This is all with the example of one type group modified modified polyethyleneimine polymers.
Formula II has narrated the modified polyethyleneimine polymers that contains the PEI skeleton, and wherein all commutable primary amine nitrogen are by using polyoxyethylene oxygen unit ,-(CH
2CH
2O)
7H replaces the hydrogen modification, and by all oxidable primary and secondary nitrogen are oxidized to the N-oxide modifying, described modified polyethyleneimine polymers has following formula to molecule subsequently:
Formula III has been narrated the modified polyethyleneimine polymers that contains the PEI skeleton, and wherein all skeleton hydrogen atoms are substituted, and some skeleton amine unit is by quaternized.Substituting group is polyoxy alkylidene oxygen unit ,-(CH
2CH
2O)
7H or methyl.The PEI soil release polymer of modification has following formula:
Formula IV has narrated the modified polyethyleneimine polymers that contains the PEI skeleton, wherein skeleton nitrogen by replace (promptly-(CH
2CH
2O)
7H or methyl), quaternized, be oxidized to N-oxide compound or their combination modification, the modified polyethyleneimine polymers that obtains has following formula:
In as above example, the nitrogen of not all unit kind contains identical modification.The present invention allows the makers-up can contain the secondary amine nitrogen of some ethoxylation, contains other secondary amine nitrogen that is oxidized to the N-oxide compound simultaneously.This is equally applicable to primary amine nitrogen, thereby, the makers-up can be chosen in oxidation or quaternized before with one or more substituting group modifications all or a part of primary amine nitrogen.Any possible combination of E group can replace primary and secondary amine nitrogen, except above-mentioned restriction.
The acid-sensitive sensitive polymeric that is used for this paper is usually in about 15% by the about 0.05%-of agglomerated particle weight, and preferably about 0.1%-is about 10%, and more preferably from about the amount of 0.2%-about 7% exists.If the acid-sensitive sensitive polymeric of this paper is a modified polyethyleneimine polymers, it is usually in about 2% by the about 0.05%-of cleaning composition weight, and preferably about 0.1%-is about 1%, and more preferably from about the content of 0.2%-about 0.8% exists.
The high-melting-point liquid that is used for this paper is unusual heavy-gravity normally, comprises that fusing point is lower than about 5 ℃, preferably is lower than about 20 ℃, more preferably less than about 50 ℃ liquid.Preferred high-melting-point liquid comprises for example acid-sensitive sensitive polymeric, nonionic and amphoterics, suds booster, anion surfactant and their mixture.The preferred high-melting-point liquid that is used for this paper comprises aforesaid modified polyamine polymers, nonionogenic tenside and tensio-active agent soup compound.
Nonionic and amphoterics as this paper high-melting-point liquid comprise C
12-C
18Alkylethoxylate (" AE ") comprises so-called narrow peak alkylethoxylate and C
6-C
12Alkylphenol alcoxylates (especially ethoxylate and blended oxyethyl group/propoxy-), C
12-C
18Trimethyl-glycine and sultaine (" Sultaines "), C
10-C
18Amine oxide etc.This paper also can use C
10-C
18N-alkyl polyhydroxy fatty acid amide.Typical example comprises C
12-C
18The N-methyl glucose amide is referring to the WO92/06154 of disclosed Cook on the 16th etc. April in 1992.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C
10-C
18N-(3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C
12-C
18Glucamide can be used for low the foaming.C
10-C
20Conventional soap also can use.High if desired foaming can be used side chain C
10-C
16Soap.Other tensio-active agent commonly used is listed in the standard article.
Anion surfactant as this paper high-melting-point liquid comprises conventional side chain and random C
10-C
20Alkyl-sulphate (" AS "), formula are CH
3(CH
2)
x(CHOSO
3 -M
+) CH
3And CH
3(CH
2)
y(CHOSO
3 -M
+) CH
2CH
3C
10-C
18Secondary (2,3) alkyl-sulphate, x and (y+1) be wherein at least about 7, preferably at least about 9 integer, M is a water-soluble cationic, especially sodium, unsaturated vitriol, for example oleyl sulfate, and C
10-C
18Alkyl alkoxy sulfate (" AE
xS ", EO1-7 ethoxy sulfate especially), C
10-C
18Alkyl alkoxy carboxylate salt (especially EO1-5 ethoxy carboxylate), C
10-18Glyceryl ether, C
10-C
18Alkyl poly glucoside and their corresponding sulfation glycan glycosides, and C
12-C
18The salt of alpha sulfonated fatty acid esters.Especially preferred coconut fat alkyl-sulphate, preferred coconut aliphatic alcohol sulfate soup compound.Other preferred anionic surfactants tensio-active agent comprises the origin source, for example the fatty alkyl vitriol that obtains of butter.
If there is and also exists acid-sensitive sensitive polymeric at this paper in anion surfactant as high-melting-point liquid, then anion surfactant neutralizes before should adding agglomeration step.Although do not plan to be limited to theory, we believe this avoided production process with store in acid-sensitive sensitive polymeric be connected degraded.
High-melting-point liquid is in about 35% by the about 0.5%-of agglomerated particle weight, and preferably about 0.5%-is about 10%, and more preferably from about the content of 0.5%-about 5% is used for this paper.
It is at least a by alkaline matter neutral acid activity material that method of the present invention also provides, and the acid activity material that is used for this paper is the sour form of anion surfactant normally.
The anion surfactant that is used for this paper generally includes the sour form of sulfonated surfactants and sulfonation surfactant.That be particularly useful herein is conventional C
11-C
18The sour form of alkylbenzene sulfonate, this alkylbenzene sulfonate can be branched-chain alkyl sulfonate, linear alkylbenzene sulfonate (" LAS ") or their mixture.
The sulfuric acid and/or the sulphonic form of required anion surfactant are provided usually, for example, can provide linear alkylbenzene sulfonate in agglomerated particle, in the method for this paper, neutralize for linear alkylbenzene sulfonate is provided.
Method of the present invention comprises adding core substance and alkaline matter and agglomerant therein step in mixing tank.The type that is used for the mixing tank of this paper comprises the soup compound mixing tank of the batch type of commercially available acquisition, for example V-mixing tank, ploughshear mixer, Fukae mixing tank etc.Method as herein described can be carried out in single mixing tank or a plurality of as required mixing tank.Specifically, moderate-speed mixers and super mixer are that this paper is preferred.
Moderate-speed mixers of the present invention is to have rotatable central shaft and some usually radially mixing tanks of the arms of extension.Be used for when of the present invention, " moderate-speed mixers " is such mixing tank, and wherein central shaft preferably is lower than about 500RPM to be lower than about 750RPM, more preferably less than the speed rotation of about 250RPM.The preferred moderate-speed mixers that is applicable to this paper is Loedige KM " colter ", and the KM mixing tank has rotary middle spindle and some arms that is extended by central shaft, has the triangle interconnecting piece that is called " plough " at the end of arm.But in mixer chamber the less blade of some high speed rotating that extend by mixer wall.Certainly, other moderate-speed mixers also can be used among the present invention, is obtained by the various sources that comprise Schugi.Equally usefully double-screw mixer is commercial as Eirich, O ' Brien and the sale of Drais mixture.The mean residence time of agglomerated particle was generally about 0.5 minute-Yue 15 minutes in moderate-speed mixers, and preferred about 2 minutes-Yue 10 minutes, more preferably from about 3 minutes-Yue 8 minutes.
The super mixer that is used for this paper can be the obtainable super mixer of any commerce/fine and close device, for example Schugi mixing tank/cyclone agglomerator or Loedige CB mixing tank.Other mixing device can be used for the present invention, can comprise conventional double-screw mixer.These and other super mixer can be obtained by many sources commercial.Be used for when of the present invention, " super mixer/fine and close device " is to have central shaft speed at least about 750RPM, more preferably at least about 1000RPM with most preferably at least about the device of 1200RPM.Being used for preferred super mixer of the present invention/fine and close device is K-G/Schugi mixing tank-cyclone agglomerator, and Schugi mixing tank-cyclone agglomerator has the centre rotational axis that has a plurality of revolving vanes that extended by central shaft and flexible outer rubber wall to prevent the particle plugging on the wall outside.The mean residence time of agglomerated particle was generally about 0.1 second-Yue 50 seconds in super mixer, and preferred about 0.1 second-Yue 30 seconds, more preferably from about 0.1 second-Yue 15 seconds.
The acid activity material that is used for this paper is usually in about 65% by the about 10%-of agglomerated particle weight, and preferably about 12%-is about 45%, and more preferably from about the content of 15%-about 35% exists.
Core substance and especially a kind of acid-sensitive sensitive polymeric very lower concentration provide, and therefore can be difficult to be dispersed in the whole mixing tank.Therefore, in preferred embodiments, provide carrier before agglomeration step, to disperse or dissolve core substance to form premixture.Since core substance normally solid or thick liquid with because core substance adds with relative low concentration, carrier help core substance is dispersed in whole particle; Be each particle within it portion contain core substance.Carrier is liquid normally, can only maybe can play dual purpose as carrier.Wherein form premixture if acid-sensitive sensitive polymeric is dispersed in, carrier is preferably non-acid, for example water.What be equally applicable to this paper is nonaqueous carrier or basic supports.
In some cases, even can cause degraded, before agglomeration process, need or mixing acid sensitive polymer and acid activity material very easily.When for example mixing tank only contained a single liquid feeding pipeline, this can take place.Therefore, in embodiments of the invention, we are surprised to find the acid activity material and itself can be used as carrier.The degraded of finding acid-sensitive sensitive polymeric is with concentration dependent and relevant with the time.Therefore, the concentration of existing acid activity material and/or acid-sensitive sensitive polymeric is big more, and DeR is fast more.Equally, the time that acid activity material and acid-sensitive sensitive polymeric exist together is long more, and it is big more to degrade.
Therefore, acid activity material itself can be used as the carrier of core substance in the method for the invention.If core substance is acid-sensitive sensitive polymeric, then very need to reduce the reaction kinetics and the degraded of acid-sensitive sensitive polymeric.Therefore, be no more than about 50% acid activity material, preferably be no more than about 25% acid activity material, the acid activity material more preferably no more than about 10% should add in the premixture.For reducing reaction times and reaction kinetics, premixture must add in the mixing tank as early as possible.Therefore, if acid activity material and acid-sensitive sensitive polymeric mix the formation premixture, premixture should preferably add in about 15 minutes in the mixing tank of agglomeration step at about 60 minutes that form premixture.In the more preferred of the inventive method, acid-sensitive sensitive polymeric is dispersed in the acid activity material to form premixture, in fact it immediately, the time of promptly about 0.1-10 second is with alkaline matter agglomeration in mixing tank.This can finish at second mixing tank of preceding outlet line or the syringe of static mixer and input agglomeration mixing tank by for example being provided with two liquid feeding pipelines and one.Therefore acid-sensitive sensitive polymeric can be dispersed in the acid activity material in this second mixing tank, and is injected into immediately in the agglomeration mixing tank.This method is particularly useful for continuous agglomeration method.
If exist, thereby must provide enough carriers to make acid-sensitive sensitive polymeric disperse easily, preferred dissolution is therein to form premixture.The weight ratio of carrier and core substance is generally at least about 1: 1 in premixture, and preferred about 1: about 8: 1 of 1-.
In preferred embodiments, method of the present invention is used for continuous agglomeration method.In typical method, at least one syringe contains core substance, and preferred acid sensitive polymer and at least one other syringe contain the acid activity material.For example, if use single agglomeration mixing tank with at least two liquid feeding pipelines, then first feeding line can contain acid-sensitive sensitive polymeric (separately or in premixture), and when alkaline matter adds fashionablely continuously, acid-sensitive sensitive polymeric is injected in the cyclone agglomerator continuously.When particle agglomeration and when becoming big, they move through mixing tank at " dirty ", and they run into second feeding line at this.Second feeding line is injected remaining acid activity material continuously, so agglomerated particle will contain the acid-sensitive sensitive polymeric that is concentrated in its inside.
In another preferred embodiment of continuation method, two isolating agglomeration mixing tanks are connected in series.Acid-sensitive sensitive polymeric adds in the alkaline matter in the first agglomeration mixing tank.Formed particle is pumped into the second agglomeration mixing tank subsequently, adds the acid activity material therein, and agglomeration process is a successive.
Hereinafter illustrate embodiments of the invention, embodiment does not limit the present invention in any way.
Embodiment 1
About 30% SODA ASH LIGHT 99.2 powder, 30%STPP, 6-8% zeolite, 4% sodium sulfate are added in 50 cubic feet of Patterson Kelly V-mixing tanks, about 1% acid-sensitive sensitive polymeric (vinylformic acid-maleic acid) is provided, be sprayed on the powder of V-mixing tank.The shell of V-mixing tank rotates with about 10-20RPM.The liquid dispersion rod is also referred to as " 1-rod " and rotates with 1200-1500RPM.Acid-sensitive sensitive polymeric is sprayed on the powder by the 1-rod.Co-agglomerated subsequently about 3 minutes of SODA ASH LIGHT 99.2 and acid-sensitive sensitive polymeric add the acid activity material in the V-mixing tank by the 1-rod subsequently.The acid activity material adds with the speed that 7-11kg/ divides.The quantity of acid activity material is about 28% of final composition by weight.The agglomerate that is obtained by the V-mixing tank cools off in fluidized bed cooler, and wherein thin product is added in the next batch charging of V-mixing tank by elutriation.The refrigerative agglomerate is sized to required particle size, is transported to the next step of method, and it is a purification step.
When being purification step, the selectivity scrubbed component, for example white dyes, enzyme, perborate and bleach activator, N for example, N, N ', N '-tetra acetyl ethylene diamine and nonanoyl oxygen base benzene sulfonate add mixing tank with agglomerate.Spices is sprayed on the agglomerate in the mixing tank to prepare final product.SODA ASH LIGHT 99.2 is excessive with the required about 4-8 stoichiometry doubly of complete neutralizing acid active substance.
Aforesaid method forms agglomerated particle, and wherein all acid-sensitive sensitive polymerics are concentrated in the inside of agglomerated particle basically.In addition, agglomerated particle has acceptable acid-sensitive sensitive polymeric stability.All percentage ratios are by final agglomerated particle weight.
Embodiment 2
Method by embodiment 1 prepares agglomerated particle, be acid-sensitive sensitive polymeric be that to contain the skeleton of the 1800MW that has an appointment and degree of ethoxylation be about 7 modified polyethyleneimine polymers.Acid-sensitive sensitive polymeric mixes in static mixer with part acid activity material immediately, is transported in the V-mixing tank.Acid activity material and acid-sensitive sensitive polymeric pump into respectively to be delivered in the static mixer.Static mixer offers the mixing rate normally 7-11kg/ minute of V-mixing tank.The ratio of acid activity material and acid-sensitive sensitive polymeric is about 1: 1 in the premixture.
Aforesaid method forms agglomerated particle, and wherein all basically acid-sensitive sensitive polymerics are concentrated in the inside of agglomerated particle.In addition, agglomerated particle has acceptable acid-sensitive sensitive polymeric stability.In the method, can find that acid-sensitive sensitive polymeric can be stabilized to the acid activity material: acid-sensitive sensitive polymeric ratio is 10: 1.
Embodiment 3
In the continuously feeding process, SODA ASH LIGHT 99.2, STPP and zeolite input super mixer (CB-Loedige 30).Acid-sensitive in the method sensitive polymeric adds the inlet charging by first liquid.Anion surfactant is imported in inlet subsequently as the acid activity material.The particle that obtains optionally vertically feeds super mixer (Schugi FX-160).Acid-sensitive sensitive polymeric also can add in this stage, if the words that it does not add in the fs.The sprinkling of acid-sensitive sensitive polymeric can be before carbonate, silicate or other spray solution.By the Schugi mixing tank (if or the Schugi mixing tank by bypass then be the CB mixing tank) agglomerate that obtains input middling speed KMLoedige (KM-600) mixing tank.Agglomerate can be with zeolite or other material efflorescence therein, and tackiness agent also injectable is gone in the KM mixing tank.For some product, the KM mixing tank can be by bypass.
In addition, all transformations of describing in the CB mixing tank can only be carried out in single KM mixing tank (no CB or Schugi).In this case, acid-sensitive sensitive polymeric injection in first inlet.Other material and tackiness agent, for example the acid activity material adds in inlet subsequently.Tackiness agent includes, but are not limited to tensio-active agent soup compound and acid activity material.For example can use nonionogenic tenside, silicate or other aqueous solution.When using the high-melting-point liquid that is used as tackiness agent, preferably their add in the core of agglomerate.In this case, they can at first add, and are subsequently to form outer field other tackiness agent.Acid-sensitive sensitive polymeric can be used as the straight polymer input mixer, or forms premixture, input mixer subsequently with water or other solvent.Choice of Solvent depends on the stability of acid-sensitive sensitive polymeric.The typical operation conditions of various mixing tanks provides following:
The representative condition of Loedige CB mixing tank (CB-30) mixing tank is as follows:
Mean residence time: 10-18 second
Tip speed: 6-13m/s
Energy state: 0.15-3.5kj/kg
The representative condition of Schugi FX-160 mixing tank is as follows:
Mean residence time: 0.1-2 second
Tip speed: 15-18m/s
Energy state: 0.15-1.0kj/kg
In the KM mixing tank, colter RPM is generally 100, and destroyer RPM is generally 1300 (mixing tank has 3 destroyers).
Aforesaid method forms agglomerated particle, and wherein all basically acid-sensitive sensitive polymerics concentrate the inside of agglomerated particle.In addition, agglomerated particle has acceptable acid-sensitive sensitive polymeric stability.
Embodiment 4
The composition of agglomerate is identical with embodiment 1.In this process, SODA ASH LIGHT 99.2, STPP, vitriol and zeolite are imported in the continuous CB-30 mixing tank.At 50% the aqueous solution of the acid-sensitive sensitive polymeric of first liquid infusion of CB inlet input, input acid activity material (LAS) in second, third and the 4th injection inlet subsequently.With the agglomerate input KM-600 that obtains, therein if desired, they use the zeolite efflorescence to keep the unrestricted flow of agglomerate.Optionally dry and cooling in fluidized-bed of the agglomerate that obtains, the fine particle of elutriation is with the constant circulation ratio input CB of 10%-80%.
The representative condition of Loedige CB mixing tank (CB-30) mixing tank is as follows:
Mean residence time: 10-18 second
Tip speed: 6-13m/s
Energy state: 0.15-3.5kj/kg
In the KM mixing tank, colter RPM is generally 100, and destroyer RPM is generally 1300 (mixing tank has 3 destroyers).
Aforesaid method forms agglomerated particle, and wherein all basically acid-sensitive sensitive polymerics concentrate the inside of agglomerated particle.In addition, agglomerated particle has acceptable acid-sensitive sensitive polymeric stability.
Embodiment 5
The composition of agglomerate is identical with embodiment 1.In this process, SODA ASH LIGHT 99.2, STPP, vitriol and zeolite are imported in the continuous KM-600 mixing tank.50% the aqueous solution at the acid-sensitive sensitive polymeric of first liquid infusion of KM inlet input.In the second and the 3rd injection inlet, inject acid activity material (LAS) subsequently.With the agglomerate input KM-600 that obtains, therein if desired, they use the zeolite efflorescence to keep the unrestricted flow of agglomerate.Optionally dry and cooling in fluidized-bed of the agglomerate that obtains.The fine particle of elutriation is with the constant circulation ratio input KM of 10%-80%.
The mixing tank condition is with identical described in the embodiment 4.
Aforesaid method forms agglomerated particle, and wherein all basically acid-sensitive sensitive polymerics are concentrated in the inside of agglomerated particle.In addition, agglomerated particle has acceptable acid-sensitive sensitive polymeric stability.
Embodiment 6
The composition of agglomerate is identical with claim 1 with method, just adds 3% high-melting-point liquid (C in acid-sensitive sensitive polymeric
12Alkylethoxylate) and 5% water to form premixture.Premixture sprays by the I-rod subsequently.
Aforesaid method forms agglomerated particle, and wherein all core substances (acid-sensitive sensitive polymeric and high-melting-point liquid) are concentrated in the inside of agglomerated particle basically.Agglomerate by aforesaid method production also has acceptable unrestricted flow character and acceptable acid-sensitive sensitive polymeric activity.
Claims (10)
1. method that forms agglomerated particle, it comprises the steps:
A., at least a alkaline matter is provided;
B., a kind of core substance is provided, and it is selected from acid-sensitive sensitive polymeric, high-melting-point liquid and their mixture;
C., at least a acid activity material is provided;
D. agglomeration alkaline matter and core substance are to form agglomerated particle in mixing tank, and it contains:
I. inner; With
Ii. outside; With
E. in mixing tank, add the acid activity material,
Wherein by in core substance adding alkaline matter that will be all basically before the acid activity material that surpasses about 50% adds mixing tank, core substance is concentrated to the inside of agglomerated particle.
2. the process of claim 1 wherein that core substance is acid-sensitive sensitive polymeric.
3. the method for claim 1, it comprises also with carrier and disperses core substance to form the step of premixture that wherein premixture formed before agglomeration step.
4. the process of claim 1 wherein that alkaline matter is selected from basic metal and alkaline earth metal carbonate, phosphoric acid salt, silicate, layered silicate, oxyhydroxide and their mixture.
5. the process of claim 1 wherein that this method is continuous agglomeration method.
6. the method for claim 2, wherein acid-sensitive sensitive polymeric contain and be equivalent to following formula before the modifications of quaternized, replacement or oxidation:
Has modified polyamine general formula V
(n+1)W
mY
nThe polyamine backbone of Z or contain and before the modification of quaternized, replacement or oxidation, be equivalent to following formula:
Has modified polyamine general formula V
(n-k+1)W
mY
nY '
kThe polyamine backbone of Z, wherein k is less than or equal to n, and described polyamine backbone had before modification greater than about 200 daltonian molecular weight, wherein
I) the V unit is the terminal units with following formula:
Ii) the W unit is the skeleton unit with following formula:
Iii) the Y unit is the chain unit with following formula:
Iv) the Z unit is the terminal units with following formula:
Wherein connect the unitary skeleton of R and be selected from C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-and their mixture; R wherein
1Be C
2-C
6Alkylidene group and their mixture; R
2Be hydrogen ,-(R
1O)
xB and their mixture; R
3Be C
1-C
18Alkyl, C
7-C
12Arylalkyl, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl and their mixture; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and their mixture; R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH-(OH) CH
2-and their mixture; R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Thiazolinyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3With their mixture; Its condition is when any E unit on the nitrogen is H, and described nitrogen neither the N-oxide compound; B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q-(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M and their mixture; M is the water-soluble cationic that hydrogen or consumption are enough to satisfy charge balance; X is a water soluble anion; M is 4-about 400; N is 0-about 200; P is 1-6, and q is 0-6; R is 0 or 1; W is 0 or 1; X is 1-100; Y is 0-100; Z is 0 or 1.
7. the method for claim 3, wherein carrier contains water.
8. the method for claim 3, wherein carrier contains about at the most 50% acid activity material.
9. the method for claim 8, wherein premixture was less than formation in about 60 minutes before adding agglomeration step.
10. method that forms agglomerated particle, it comprises the steps:
A., at least a alkaline matter is provided;
B., at least a acid-sensitive sensitive polymeric is provided;
C., at least a acid activity material is provided;
D., at least a carrier is provided;
E. in carrier, disperse acid-sensitive sensitive polymeric to form premixture;
F. agglomeration alkaline matter and premixture are to form agglomerated particle in mixing tank, and it contains:
I. inner; With
Ii. outside; With
G. in mixing tank, add the acid activity material,
Wherein by before the acid activity material that surpasses about 50% adds mixing tank all basically acid-sensitive sensitive polymerics being gone in the alkaline matter, acid-sensitive sensitive polymeric is concentrated to the inside of agglomerated particle; Wherein acid-sensitive sensitive polymeric contains and be equivalent to following formula before the modification of quaternized, replacement or oxidation:
Has modified polyamine general formula V
(n+1)W
mY
nThe polyamine backbone of Z or contain and before the modification of quaternized, replacement or oxidation, be equivalent to following formula:
Has modified polyamine general formula V
(n-k+1)W
mY
nY '
kThe polyamine backbone of Z, wherein k is less than or equal to n, and described polyamine backbone had before modification greater than about 200 daltonian molecular weight, wherein
I) the V unit is the terminal units with following formula:
Ii) the W unit is the skeleton unit with following formula:
Iii) the Y unit is the chain unit with following formula:
Iv) the Z unit is the terminal units with following formula:
Wherein connect the unitary skeleton of R and be selected from C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-and their mixture; R wherein
1Be C
2-C
6Alkylidene group and their mixture; R
2Be hydrogen ,-(R
1O)
xB and their mixture; R
3Be C
1-C
18Alkyl, C
7-C
12Arylalkyl, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl and their mixture; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and their mixture; R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-and their mixture; R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Thiazolinyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3With their mixture; Its condition is when any E unit on the nitrogen is H, and described nitrogen neither the N-oxide compound; B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q-(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M and their mixture; M is the water-soluble cationic that hydrogen or consumption are enough to satisfy charge balance; X is a water soluble anion; M is 4-about 400; N is 0-about 200; P is 1-6, and q is 0-6; R is 0 or 1; W is 0 or 1; X is 1-100; Y is 0-100; Z is 0 or 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1998/025229 WO2000031234A1 (en) | 1998-11-25 | 1998-11-25 | Process for forming an agglomerated particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1344313A true CN1344313A (en) | 2002-04-10 |
| CN1216138C CN1216138C (en) | 2005-08-24 |
Family
ID=22268374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98814325.9A Expired - Fee Related CN1216138C (en) | 1998-11-25 | 1998-11-25 | Process for forming agglomerated particle |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP1133550B1 (en) |
| JP (1) | JP2002530518A (en) |
| CN (1) | CN1216138C (en) |
| AR (1) | AR021385A1 (en) |
| AT (1) | ATE226628T1 (en) |
| AU (1) | AU1799599A (en) |
| BR (1) | BR9816087A (en) |
| CA (1) | CA2347810A1 (en) |
| DE (1) | DE69808972T2 (en) |
| ES (1) | ES2182386T3 (en) |
| MX (1) | MX218942B (en) |
| PH (1) | PH11999002971B1 (en) |
| WO (1) | WO2000031234A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6514929B1 (en) * | 1998-11-25 | 2003-02-04 | The Procter & Gamble Company | Process for forming an agglomerated particle |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8512638D0 (en) * | 1985-05-18 | 1985-06-19 | Procter & Gamble | Laundry detergent compositions |
| GB9226942D0 (en) * | 1992-12-24 | 1993-02-17 | Procter & Gamble | Dispersing agent |
| WO1998014550A1 (en) * | 1996-10-04 | 1998-04-09 | The Procter & Gamble Company | Process for making a low density detergent composition |
| AU7527096A (en) * | 1996-11-01 | 1998-05-29 | Procter & Gamble Company, The | Color care compositions |
-
1998
- 1998-11-25 AT AT98962843T patent/ATE226628T1/en not_active IP Right Cessation
- 1998-11-25 CN CN98814325.9A patent/CN1216138C/en not_active Expired - Fee Related
- 1998-11-25 ES ES98962843T patent/ES2182386T3/en not_active Expired - Lifetime
- 1998-11-25 AU AU17995/99A patent/AU1799599A/en not_active Abandoned
- 1998-11-25 BR BR9816087-7A patent/BR9816087A/en not_active IP Right Cessation
- 1998-11-25 MX MXPA01005246 patent/MX218942B/en unknown
- 1998-11-25 JP JP2000584045A patent/JP2002530518A/en not_active Withdrawn
- 1998-11-25 CA CA002347810A patent/CA2347810A1/en not_active Abandoned
- 1998-11-25 DE DE69808972T patent/DE69808972T2/en not_active Expired - Fee Related
- 1998-11-25 WO PCT/US1998/025229 patent/WO2000031234A1/en active IP Right Grant
- 1998-11-25 EP EP98962843A patent/EP1133550B1/en not_active Expired - Lifetime
-
1999
- 1999-11-24 AR ARP990105981A patent/AR021385A1/en active IP Right Grant
- 1999-11-25 PH PH11999002971A patent/PH11999002971B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| MXPA01005246A (en) | 2001-08-01 |
| CN1216138C (en) | 2005-08-24 |
| EP1133550B1 (en) | 2002-10-23 |
| DE69808972T2 (en) | 2003-06-18 |
| ATE226628T1 (en) | 2002-11-15 |
| DE69808972D1 (en) | 2002-11-28 |
| AR021385A1 (en) | 2002-07-17 |
| MX218942B (en) | 2004-02-03 |
| PH11999002971B1 (en) | 2005-01-07 |
| BR9816087A (en) | 2001-08-14 |
| JP2002530518A (en) | 2002-09-17 |
| AU1799599A (en) | 2000-06-13 |
| EP1133550A1 (en) | 2001-09-19 |
| CA2347810A1 (en) | 2000-06-02 |
| WO2000031234A1 (en) | 2000-06-02 |
| ES2182386T3 (en) | 2003-03-01 |
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