CN1764373A - 制备水分散性颗粒剂的方法 - Google Patents
制备水分散性颗粒剂的方法 Download PDFInfo
- Publication number
- CN1764373A CN1764373A CNA2004800078871A CN200480007887A CN1764373A CN 1764373 A CN1764373 A CN 1764373A CN A2004800078871 A CNA2004800078871 A CN A2004800078871A CN 200480007887 A CN200480007887 A CN 200480007887A CN 1764373 A CN1764373 A CN 1764373A
- Authority
- CN
- China
- Prior art keywords
- agricultural chemical
- chemical activity
- activity composition
- sodium salt
- pyrroles
- 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
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 239000004562 water dispersible granule Substances 0.000 title description 2
- 239000007788 liquid Substances 0.000 claims abstract description 50
- 239000003905 agrochemical Substances 0.000 claims abstract description 29
- 239000008187 granular material Substances 0.000 claims abstract description 17
- 238000005054 agglomeration Methods 0.000 claims abstract description 13
- 230000002776 aggregation Effects 0.000 claims abstract description 13
- 239000000969 carrier Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 35
- 230000000694 effects Effects 0.000 claims description 26
- -1 methyl ester sodium salt Chemical class 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007921 spray Substances 0.000 claims description 17
- 239000004009 herbicide Substances 0.000 claims description 16
- 241000196324 Embryophyta Species 0.000 claims description 15
- GOIGHUHRYZUEOM-UHFFFAOYSA-N [S].[I] Chemical compound [S].[I] GOIGHUHRYZUEOM-UHFFFAOYSA-N 0.000 claims description 15
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical class CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 15
- 150000003233 pyrroles Chemical class 0.000 claims description 15
- 239000005507 Diflufenican Substances 0.000 claims description 11
- WYEHFWKAOXOVJD-UHFFFAOYSA-N diflufenican Chemical compound FC1=CC(F)=CC=C1NC(=O)C1=CC=CN=C1OC1=CC=CC(C(F)(F)F)=C1 WYEHFWKAOXOVJD-UHFFFAOYSA-N 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical compound OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 claims description 4
- DQKWXTIYGWPGOO-UHFFFAOYSA-N (2,6-dibromo-4-cyanophenyl) octanoate Chemical compound CCCCCCCC(=O)OC1=C(Br)C=C(C#N)C=C1Br DQKWXTIYGWPGOO-UHFFFAOYSA-N 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims 1
- 238000001694 spray drying Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 6
- 238000005507 spraying Methods 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 3
- 239000011814 protection agent Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000002363 herbicidal effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- RMFGNMMNUZWCRZ-UHFFFAOYSA-N Humulone Natural products CC(C)CC(=O)C1=C(O)C(O)(CC=C(C)C)C(O)=C(CC=C(C)C)C1=O RMFGNMMNUZWCRZ-UHFFFAOYSA-N 0.000 description 3
- 229940100389 Sulfonylurea Drugs 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- VMSLCPKYRPDHLN-NRFANRHFSA-N humulone Chemical compound CC(C)CC(=O)C1=C(O)C(CC=C(C)C)=C(O)[C@@](O)(CC=C(C)C)C1=O VMSLCPKYRPDHLN-NRFANRHFSA-N 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UWVKRNOCDUPIDM-UHFFFAOYSA-N Ethoxysulfuron Chemical compound CCOC1=CC=CC=C1OS(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 UWVKRNOCDUPIDM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000013066 combination product Substances 0.000 description 2
- 229940127555 combination product Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- IRCMYGHHKLLGHV-UHFFFAOYSA-N 2-ethoxy-3,3-dimethyl-2,3-dihydro-1-benzofuran-5-yl methanesulfonate Chemical compound C1=C(OS(C)(=O)=O)C=C2C(C)(C)C(OCC)OC2=C1 IRCMYGHHKLLGHV-UHFFFAOYSA-N 0.000 description 1
- IDGRPSMONFWWEK-UHFFFAOYSA-N 2-ethylhexyl 2-(4-chloro-2-methylphenoxy)acetate Chemical group CCCCC(CC)COC(=O)COC1=CC=C(Cl)C=C1C IDGRPSMONFWWEK-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000003666 Amidosulfuron Substances 0.000 description 1
- CTTHWASMBLQOFR-UHFFFAOYSA-N Amidosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)N(C)S(C)(=O)=O)=N1 CTTHWASMBLQOFR-UHFFFAOYSA-N 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- FUWXCBQJKGNLNU-UHFFFAOYSA-N C1=CC=CC=C1.O1C=NC=C1 Chemical compound C1=CC=CC=C1.O1C=NC=C1 FUWXCBQJKGNLNU-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 239000005946 Cypermethrin Substances 0.000 description 1
- 239000005503 Desmedipham Substances 0.000 description 1
- 239000005512 Ethofumesate Substances 0.000 description 1
- PQKBPHSEKWERTG-UHFFFAOYSA-N Fenoxaprop ethyl Chemical compound C1=CC(OC(C)C(=O)OCC)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 PQKBPHSEKWERTG-UHFFFAOYSA-N 0.000 description 1
- 239000005785 Fluquinconazole Substances 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005579 Metamitron Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000005588 Oxadiazon Substances 0.000 description 1
- CHNUNORXWHYHNE-UHFFFAOYSA-N Oxadiazon Chemical compound C1=C(Cl)C(OC(C)C)=CC(N2C(OC(=N2)C(C)(C)C)=O)=C1Cl CHNUNORXWHYHNE-UHFFFAOYSA-N 0.000 description 1
- 239000005594 Phenmedipham Substances 0.000 description 1
- 239000005822 Propiconazole Substances 0.000 description 1
- 239000005601 Propoxycarbazone Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- HBCBJXOSTRIDAQ-UHFFFAOYSA-N [S].NC=O Chemical compound [S].NC=O HBCBJXOSTRIDAQ-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001720 action spectrum Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- CYOOVEAWXNAHJA-UHFFFAOYSA-N azane;phosphane Chemical compound N.N.P CYOOVEAWXNAHJA-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 1
- 229960005424 cypermethrin Drugs 0.000 description 1
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 description 1
- WZJZMXBKUWKXTQ-UHFFFAOYSA-N desmedipham Chemical compound CCOC(=O)NC1=CC=CC(OC(=O)NC=2C=CC=CC=2)=C1 WZJZMXBKUWKXTQ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000009477 fluid bed granulation Methods 0.000 description 1
- IJJVMEJXYNJXOJ-UHFFFAOYSA-N fluquinconazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1N1C(=O)C2=CC(F)=CC=C2N=C1N1C=NC=N1 IJJVMEJXYNJXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VHCNQEUWZYOAEV-UHFFFAOYSA-N metamitron Chemical compound O=C1N(N)C(C)=NN=C1C1=CC=CC=C1 VHCNQEUWZYOAEV-UHFFFAOYSA-N 0.000 description 1
- JTHMVYBOQLDDIY-UHFFFAOYSA-N methyl 2-[(4-methyl-5-oxo-3-propoxy-1,2,4-triazole-1-carbonyl)sulfamoyl]benzoate Chemical compound O=C1N(C)C(OCCC)=NN1C(=O)NS(=O)(=O)C1=CC=CC=C1C(=O)OC JTHMVYBOQLDDIY-UHFFFAOYSA-N 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- IDOWTHOLJBTAFI-UHFFFAOYSA-N phenmedipham Chemical compound COC(=O)NC1=CC=CC(OC(=O)NC=2C=C(C)C=CC=2)=C1 IDOWTHOLJBTAFI-UHFFFAOYSA-N 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- BACHBFVBHLGWSL-JTQLQIEISA-N rac-diclofop methyl Natural products C1=CC(O[C@@H](C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-JTQLQIEISA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- RFOHRSIAXQACDB-UHFFFAOYSA-M sodium;2-(2,4-dichlorophenoxy)acetate Chemical compound [Na+].[O-]C(=O)COC1=CC=C(Cl)C=C1Cl RFOHRSIAXQACDB-UHFFFAOYSA-M 0.000 description 1
- QGKPUZOFTJQTHL-UHFFFAOYSA-M sodium;4-cyano-2,6-diiodophenolate Chemical class [Na+].[O-]C1=C(I)C=C(C#N)C=C1I QGKPUZOFTJQTHL-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/16—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by suspending the powder material in a gas, e.g. in fluidised beds or as a falling curtain
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明涉及一种制备水分散性植物保护颗粒剂的方法，该方法包含以下步骤，A.将两种或多种单个液流喷洒进团聚装置中，其中a)至少一种包含一种或多种熔点为120℃或更高的农业化学活性成分的液流，和b)至少一种包含一种或多种熔点低于120℃的农业化学活性成分的液流和一种或多种载体，并且B.进行团聚。
Description
本发明涉及植作物保护制剂领域。特别是，本发明涉及一种制备水分散性植物保护颗粒剂(WG)的方法。
通常，用于植物保护的活性成分不以纯物质的形式使用。根据使用区域和使用种类，以及物理、化学和生物参数，活性成分与常规助剂和添加剂相混合以活性成分制剂来使用。与其它活性成分相组合，例如以扩展作用谱和/或保护作物(例如通过与安全剂相组合)也是已知的。优点是例如易于操作、降低施用错误剂量的危险和降低生产成本。
若组合物以颗粒剂施用，会产生不期望的接触作用，例如在液体组分或低熔点组分与高熔点组分一起存在时的情形下。这会导致形成让操作、测量和计量更加困难的粘结或结块。此外，在制剂是不溶于水的组合物并且在喷雾桶中迅速均一分散是至关重要的情形下，则在容器底部和主滤器或喷嘴过滤器前会形成沉淀。
桶混方法避免了当液体组分或低熔点组分与高熔点组分接触会产生的上述缺点。
然而已知的是，相比组合产品来说，用分别计量和所配制的空容器处理单个包装单元是不利的。然而该问题通过已知的双组分(Twin-Pack)溶液基本上得以避免，这类溶液带来有关研制、生产和品质保证的附加的复杂性。因此，尝试着制备组合产品。
因此，WO 97/20467描述了将高分散性二氧化硅作为液相吸收基质的用途，目的在于保护避免与乙氧嘧磺隆接触。在该情形下，最终产品是通过挤出所有组分的湿润混合物来制备的。该方法的缺点在于，当湿预混物通入挤出工具(例如筛子)时，形成压力，从而将吸附的液体或半可塑性混合物从载体材料中挤压出来，在颗粒相中产生了不期望的不可逆的桥结现象。结果是降低了产品在水中的悬浮度并且在农业施用装置中出现了不受欢迎的滤渣。
另一种制备颗粒形式产品的方法是流化床粒化(流化床团聚)，其中较小的压力作用于材料以进行粒化(EP-A-0757891、EP-A-611593、EP-A-821618、US5,883,047)。WO 98/42192描述了一种制备农业化学产品的方法，其中以共同的浆液将磺酰脲和低熔点助剂用高分散硅酸钙进行配制，并且采用双物质喷嘴法以流化床层造粒。此外该方法的缺点在于，由于其是以共同的乳液和/或悬浮液加工的，不同部分彼此间有不利的相互作用。此处，低熔点组分从其多孔载体上可被乳化或洗涤出来，并且与微粒组分相接触，这导致已知的缺点。
本发明的目的在于提供一种制备高和低熔点农业化学活性成分的混合物的水分散性植物保护颗粒剂的改良方法。出人意外地，已发现该目的可以通过本发明的方法来实现。
因此，本发明涉及一种制备水分散性植物保护颗粒剂的方法，该方法包含以下步骤，
A.将两种或多种单个液流喷洒进团聚装置中，其中
a)至少一种包含一种或多种熔点为大于等于120℃的农业化学活性成分的液流，和
b)至少一种包含一种或多种熔点低于120℃的农业化学活性成分的液流和一种或多种载体，并且
B.进行团聚。
术语植物保护颗粒剂应理解为指包含农业化学活性成分的颗粒剂。用于制备本发明颗粒剂的方法和装置描述于例如H.Mollet，A.Grubenmann，Formulierungstechnik，Verlag Wiley-VCH，2000中，在此将其第6.2章引入本说明书。对于本发明而言，尤其适宜的颗粒剂是由干筛分析测得的粒径为50至10000，优选100至1000，尤其优选200至900微米的疏松材料。测定颗粒质量的方法描述于例如CIPACHandbook，Vol.F，Herausgeber：Collaborative InternationalPesticides Analytical Council Ltd.(1995)中。水分散性植物保护颗粒剂描述于例如H.Mollet，A.Grubenmann，Formulierungstechnik，Verlag Wiley-VCH，2000，章节14.2.3中，因此其被引入本说明书。
在本发明的方法中，将两种或多种单个液流一并喷洒进团聚装置中。在喷洒过程中液流优选为室温，并且通常在压力为2-10巴、优选4-6巴的压力下喷洒。
喷洒可以利用例如两个或多个双物质喷嘴，或利用一个或多个三或多物质喷嘴来进行。
双物质喷嘴是这样构成的，将组成喷雾相的液流置于由气流(例如空气或氮气)的包封流环绕的喷嘴出口处，其被集中作用成液流，并且在喷嘴出口处分散成细小的喷雾滴(参见，例如H.Mollet，A.Grubenmann，Formulierungstechnik，Verlag Wiley-VCH，2000，219页)。
三或多物质喷嘴是这样构成的，将组成喷雾相的两种或三种单个液流置于由一种或多种气流(例如空气或氮气)的包封流环绕的喷嘴出口处，其被集中作用成一种或多种液流，并且在喷嘴出口处分散成细小的喷雾滴(参见，例如EP-A-611593)。
在优选的实施方式中，将两种不同液流一液流a)和液流b)进行喷洒。此处，液流a)和b)可以采用两个分开的双物质喷嘴进行喷洒，即利用双物质喷嘴α)喷洒液流a)，利用双物质喷嘴β)喷洒b)。在优选的实施方式中，将两种液流a)和b)采用三物质喷嘴一并喷洒。
为优化该方法，在团聚装置中，也可以利用多个相同对的双物质喷嘴α)，β)，或多个相同的三或多物质喷嘴来进行喷洒。
液流可以在本领域技术人员已知的团聚装置中喷洒(参见，例如H.Mollet，A.Grubenmann，Formulierungstechnik，Verlag Wiley-VCH，2000，第6.2.5、6.2.7和6.2.8章)。这类团聚装置的实例描述于例如EP-A-0757891、EP-A-611 593、EP-A-821 618、US 5,883,047和WO 98/42192中。
多种本领域技术人员已知的团聚方法可用于进行团聚(参见，例如H.Mollet，A.Grubenmann，Formulierungstechnik，Verlag Wiley-VCH，2000，第6.2.5、6.2.7和6.2.8章)，部分方法在下列实施例中描述。
从而，团聚可以通过例如喷洒干燥来进行，其中液流a)和b)通过两个或多个双物质喷嘴或通过一个或多个三或多物质喷嘴喷洒成足够长的、垂直下落区域。最终的液滴在下落过程中干燥一优选利用热生产气流(例如空气或氮气)，并且以细颗粒团聚和到达装置底部。适用于该目的的装置是例如由Niro制造的，如Niro雾化器类。
优选的实施方式是流化床团聚，其中液流a)和b)通过两个或多个双物质喷嘴或通过一个或多个三或多物质喷嘴喷洒进入容器中(团聚器)，优选该容器最初是空的并且逆着重力有连续的热生产气流(例如空气或氮气)通过其中。由于生产气流的缘故，最终液滴变干并且保持在持久的悬浮状态(流化床)。作为液流的第一体积部分的最初产物的细颗粒保留在流化床中，并且由于从沉降于其上的液流的随后体积部分形成液滴并且干燥，其用作核芯形成更大颗粒(团聚)。从而可以获得粒径大至毫米级的颗粒。用于流化床团聚的装置例如由Aeromatic制造，例如用于工艺实验室的MP-1类型。
本发明的方法可以连续或分批进行。除农业化学活性成分外，在本发明方法中所喷洒的液流a)和b)包含作为连续相的水。其它组分，例如通常用于植物保护中的溶剂或助剂和添加剂，例如肥料(例如由BASF制造的Nitrophoska)或制剂助剂如抗漂浮剂、保湿剂、表面活性剂如甜菜碱类或聚合表面活性剂、分散剂、湿润剂、乳化剂、稳定剂如pH稳定剂、UV稳定剂、消泡剂、合成或天然聚合物、或增效剂如Genapol系列(例如Genapol X-100)可以任选的存在。
为制备液体a)和b)，组分可以根据已知方法彼此进行混合，例如采用搅拌或一起研磨所有的或部分组分。
本发明适宜的农业化学活性成分是例如除草剂、杀真菌剂(例如氟喹唑、丙环唑)、杀虫剂(例如溴氰菊酯、氯氰菊酯)、安全剂或植物生长调节剂(例如Thidiazurone)。本说明书所提及的农业化学活性成分通常是已知的，例如公开在“农药手册(The PesticideManual)”British Crop Protection Council，Herausgeber：CDSTomlin中。农业化学活性成分的熔点是根据差热分析来测定。
如果农业化学活性成分是在本申请中所提及的，其始终应理解为不仅指中性化合物，而且还包括其与无机和/或有机抗衡离子的盐。因此，例如磺酰脲类可形成例如盐，其中-SO2-NH-基团的氢被农业上有用的阳离子所取代。这类盐例如金属盐，尤其是碱金属或碱土金属盐，尤其是钠盐或钾盐，或其它的铵盐，或与有机胺的盐。同样地，盐形成会发生酸附着至碱基团如氨基和烷基氨基。适用于此的酸是强无机和有机酸，例如HCl、HBr、H2SO4或HNO3。
液流a)包含一种或多种熔点高于120℃的农业化学活性成分。在优选的实施方式中，适宜的熔点高于120℃的农业化学活性成分是除草剂如(熔点在括号中给出)：
磺酰脲类，例如甲酰氨磺隆(199℃)及其盐如钠盐、叠磺隆及其盐和酯如叠磺隆甲酯钠盐(189℃)、碘磺隆及其盐和酯如碘磺隆加至及其盐，例如碘磺隆甲酯钠盐(152℃)、乙氧嘧磺隆(144℃)和酰嘧磺隆(160℃)、Propoxycarbazone(230℃)、溴苯腈-苯酚(194℃)、溴苯腈钾盐(360℃)、碘苯腈-苯酚(212℃)、碘苯腈钠盐(360℃)、吡氟酰草胺(159℃)、2，4-D酸(141℃)、2，4-D钠盐、异噁唑草酮(140℃)、磺草酮(139℃)、草甘膦(189℃)、草铵膦铵盐(215℃)、甜菜宁(143℃)、甜菜安(120℃)、苯嗪草酮(167℃)和丙炔噁草酮(131℃)。
优选地，液流a)包含至少一种农业化学活性成分如熔点为120℃或更高并且微溶于水，例如在标准条件下测得低于1000mg/l，优选低于100mg/l，尤其优选低于10mg/l的除草剂。在优选的实施方式中，这些具有高熔点和微溶于水的农业化学活性成分是以细磨成所定义大小的形式来使用的，由干筛分析测定的粒径通常为1-20微米，优选为2-10微米，尤其优选为3-8微米。
此外，液流a)还包含水和任选的其它组分如通常用于植物保护中的助剂和添加剂，尤其是分散剂、消泡剂和湿润剂；载体也同样可以存在。
液流b)包含一种或多种熔点低于120℃、优选90℃或更低的农业化学活性成分。该农业化学活性成分也可以以溶解形式使用。
在优选的实施方式中，熔点低于120℃的适宜农业化学活性成分是除草剂和安全剂例如(熔点示于括号中)：
吡咯二酸二乙酯(50℃)、双苯噁唑酸乙酯(86℃)、溴苯腈辛酸酯(45℃)、碘苯腈辛酸酯(59℃)、MCPA 2-乙基己基、精噁唑禾草灵乙酯(89℃)、禾草灵甲酯(118℃)、溴苯腈丁酸酯(90℃)、乙氧呋草黄(70℃)和Oxadiazon(87℃)。
存在于液流b)和任选也存在于液流a)中的载体是固体。所述载体通常是已知的，例如已知于：W.van Falkenburg(Hrsg.)，农药制剂(Pesticide Formulations)，Marcel Dekker，Inc.，New York，1973；或已知于：Schriftenreihe Degussa Nr.1，Synthetische Kieselsurenfür Pflanzenschutz-und Schdlingsbekmpfungsmittel，Mrz 1989。它们也是商购可得的。
优选的载体是例如无机或有机载体如纤维素及其衍生物，例如Tylose、Tylopur、Methylan和Finnix，淀粉及其衍生物如Maizena和Mondamin，或硅酸盐如高岭土、膨润土、滑石、叶蜡石、硅藻土和沉淀二氧化硅，例如Sipernat(例如Sipernat50S或Sipernat500 LS)，Dessalon、Aerosil、Silkasil或Ketiensil。
液流b)还包含水。其它组分如有机溶剂，例如饱和或不饱和的脂肪族溶剂(例如白油)、芳香族溶剂(例如Solvesso100、Solvesso150或Solvesso200或二甲苯)、植物油及其酯交换产物(例如菜籽油和菜籽油甲酯)或脂肪族羧酸酯(例如RhodiasolvRDPE)或芳香族羧酸酯(例如苯甲酸苄酯)，以及通常用于作物保护中的助剂和添加剂如乳化剂也可以任选地存在。
本发明还涉及由本发明方法所获得的水分散性植物保护颗粒剂。该颗粒具有显著的性能特征如在喷雾桶中的分解性、喷雾混合物的稳定性和能穿过滤网。
本发明优选的颗粒剂包含下列两个或多个农业化学活性成分的组合：吡氟酰草胺+吡咯二酸二乙酯、碘磺隆甲酯钠盐+吡氟酰草胺+吡咯二酸二乙酯、叠磺隆甲酯+碘磺隆甲酯钠盐+吡氟酰草胺+吡咯二酸二乙酯、叠磺隆甲酯钠盐+碘磺隆甲酯钠盐+吡氟酰草胺+吡咯二酸二乙酯、碘磺隆甲酯钠盐+吡咯二酸二乙酯+溴苯腈辛酸酯或碘磺隆甲酯钠盐+吡咯二酸二乙酯+溴苯腈丁酸酯。
下面的工艺实施例意旨说明本发明并且不对特征作任何限制。
A.实施例
1.制备液体
液体a)
将1082g吡氟酰草胺、640g高岭土、363g的MorwetD 425、98g的HostapurOSB、63g的KuviskolK30和6g的消泡粉末ASP13搅拌引入4.71的水中。在Dyno-Mill KDL Pilot(d40 4μm)型球磨机中研磨浆液。随后将69g叠磺隆甲酯钠盐和23g碘磺隆甲酯钠盐搅拌引入所得分散液中。
液体b)
用0.21水将151g的Sipernat50S制成浆液，并且搅拌引入202g吡咯二酸二乙酯、19g的分散剂Emulsogen3510和14gPhenylsulfonatCa的209g Solvesso200ND溶液。随后，将混合物于室温下搅拌30分钟。
2.流化床团聚
将两种液体a)和b)通过三物质喷嘴喷洒在Aeromatic MP1流化床团聚设备中。液体a)以9.6l/h喷洒，相当于4690g填充/h，而液体b)以2.4l/h喷洒，相当于1190g填充/h。生产气体的量为50m3/h，气体引入温度为135℃，并且产品温度为50℃。其产率为2.5kg流动颗粒。性能特征根据CIPAC方法来检验(CIPAC Handbook，Vol.F，Herausgeber：CollaboratiVe International PesticidesAnalytical Council Ltd.(1995))并且获得如下结果：分散度(CIPACMT174)：87％，悬浮度(CIPAC MT161)：85％，湿筛试验(CIPAC MT59)：于150μm上残余0.24％。
B.对比实施例
将由793.8g吡氟酰草胺、50.8g叠磺隆甲酯钠盐、16.7g碘磺隆甲酯钠盐、470g高岭土、266g MorwetD 425、71.7g的HostapurOSB、46.2g的LuviskolK30和4.6g的消泡剂粉末ASP13和148.3g吡咯二酸二乙酯的吸收溶液、13.9g分散剂Emulsogen3510和在111g Sipernat50S上的于154g Solvesso200中的10.1g PhenylsulfonatCa的预混物搅拌引入4.31水中，并且在Dyno-Mill KDL Pilot(d50＝4μm)型球磨机中磨细。在流化床团聚设备(Aeromatic MP1)中利用双物质喷嘴喷洒所得浆液。生产气体的量为42m3/h和8kg的喷洒液体/h，引入气体的温度为140℃，产品温度为55℃，制得2.4kg的流动颗粒。由CIPAC方法检验所得产品的性能特征是：分散度(CIPAC MT174)：42％，悬浮度(CIPAC MT161)：30％，湿筛试验(CIPAC MT59)：于150μm上残余12％。
Claims (11)
1.一种制备水分散性植物保护颗粒剂的方法，该方法包含以下步骤，
A.将两种或多种单个液流喷洒进团聚装置中，其中
a)至少一种包含一种或多种熔点为120℃或更高的农业化学活性成分的液流，和
b)至少一种包含一种或多种熔点低于120℃的农业化学活性成分的液流和一种或多种载体，并且
B.进行团聚。
2.根据权利要求1的方法，其中液流是利用一个或多个双物质喷嘴或利用一个或多个三或多物质喷嘴来喷洒的。
3.根据权利要求1或2的方法，其中喷洒两种不同的液流。
4.根据权利要求1至3一项或多项所述的方法，其中团聚装置是喷雾干燥装置或流化床团聚装置。
5.根据权利要求1至4一项或多项所述的方法，其中液流a)和b)包含水。
6.根据权利要求1至5一项或多项所述的方法，其中液流a)包含作为农业化学活性成分的一种或多种除草剂。
7.根据权利要求1至6一项或多项所述的方法，其中液流b)包含作为农业化学活性成分的一种或多种除草剂和/或一种或多种安全剂。
8.由权利要求1至7一项或多项所述方法获得的水分散性植物保护颗粒剂。
9.根据权利要求8的水分散性植物保护颗粒剂，其包含a)一种或多种熔点为120℃或更高的农业化学活性成分，b)一种或多种熔点低于120℃的农业化学活性成分，和c)一种或多种载体。
10.根据权利要求8或9所述的水分散性植物保护颗粒剂，其包含a)作为农业化学活性成分的熔点为120℃或更高的一种或多种除草剂，和b)作为农业化学活性成分的熔点低于120℃的一种或多种除草剂和/或一种或多种安全剂。
11.根据权利要求8至10一项或多项所述的水分散性植物保护颗粒剂，其包含作为农业化学活性成分的吡氟酰草胺+吡咯二酸二乙酯、碘磺隆甲酯钠盐+吡氟酰草胺+吡咯二酸二乙酯、叠磺隆甲酯+碘磺隆甲酯钠盐+吡氟酰草胺+吡咯二酸二乙酯、叠磺隆甲酯钠盐+碘磺隆甲酯钠盐+吡氟酰草胺+吡咯二酸二乙酯、碘磺隆甲酯钠盐+吡咯二酸二乙酯+溴苯腈辛酸酯或碘磺隆甲酯钠盐+吡咯二酸二乙酯+溴苯腈丁酸酯。
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| DE10307078.8 | 2003-02-19 | ||
| DE10307078A DE10307078A1 (de) | 2003-02-19 | 2003-02-19 | Verfahren zur Herstellung von wasserdispergierbaren Granulaten |
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| CN100333640C CN100333640C (zh) | 2007-08-29 |
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| EP (1) | EP1596654A1 (zh) |
| JP (1) | JP2006517935A (zh) |
| KR (1) | KR20050102662A (zh) |
| CN (1) | CN100333640C (zh) |
| AU (1) | AU2004212689A1 (zh) |
| BR (1) | BRPI0407639A (zh) |
| CA (1) | CA2516416A1 (zh) |
| DE (1) | DE10307078A1 (zh) |
| EA (1) | EA008142B1 (zh) |
| MX (1) | MXPA05008870A (zh) |
| WO (1) | WO2004073403A1 (zh) |
| ZA (1) | ZA200506603B (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101980600A (zh) * | 2008-02-05 | 2011-02-23 | 北美爱利思达生命科学有限责任公司 | 低熔点活性化合物的固体制剂 |
| CN103651341A (zh) * | 2013-12-27 | 2014-03-26 | 山东省农药科学研究院 | 含百草枯二氯化物的颗粒剂及其制备方法 |
| CN103766346A (zh) * | 2013-12-27 | 2014-05-07 | 山东省农药科学研究院 | 含百草枯二氯化物的水分散性颗粒剂及其制备方法 |
| CN116806821A (zh) * | 2023-06-27 | 2023-09-29 | 山东京博农化科技股份有限公司 | 一种包含高熔点原药和低熔点原药的水分散粒剂的加工方法 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004047927A1 (de) † | 2004-10-01 | 2006-04-06 | Bayer Cropscience Gmbh | Wässrige Dispersionen enthaltend Diflufenican |
| EP1836894A1 (de) * | 2006-03-25 | 2007-09-26 | Bayer CropScience GmbH | Neue Sulfonamid-haltige feste Formulungen |
| CN101262770A (zh) * | 2005-09-08 | 2008-09-10 | 拜尔作物科学股份公司 | 新型的含磺酰胺的固体配制剂 |
| EP1947946A2 (de) * | 2005-09-08 | 2008-07-30 | Bayer Cropscience Ag | Neue sulfonamid-haltige feste formulierungen |
| EP1902618A1 (de) * | 2006-08-17 | 2008-03-26 | Bayer CropScience AG | Verfahren zur Herstellung von Sulfonamidsalzen |
| EP2147600A1 (en) | 2008-07-21 | 2010-01-27 | Bayer CropScience AG | Method for weed control in lawn |
| CN110529310B (zh) * | 2019-09-24 | 2024-04-02 | 西华大学 | 一种高熔点脂肪酸甲酯或乙酯供油系统 |
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|---|---|---|---|---|
| FR2591069B1 (fr) * | 1985-12-09 | 1988-03-18 | Produits Ind Cie Fse | Produits herbicides a base d'esters de bromoxynil et/ou d'ioxynil |
| DE3918288A1 (de) * | 1989-06-05 | 1990-12-06 | Hoechst Ag | Herbizide mittel |
| US5230892A (en) * | 1990-08-24 | 1993-07-27 | Bayer Aktiengesellschaft | Solid formulations |
| DE4120694A1 (de) * | 1990-08-24 | 1992-02-27 | Bayer Ag | Feststoff-formulierungen |
| RO117587B1 (ro) * | 1991-07-12 | 2002-05-30 | Hoechst Ag | Compozitie erbicida, procedeu de obtinere a acesteia si metoda pentru controlul plantelor nedorite |
| CN1074646C (zh) * | 1992-10-06 | 2001-11-14 | 国际壳牌研究有限公司 | 除草剂混合物 |
| DE4304405A1 (de) * | 1993-02-15 | 1994-08-18 | Bayer Ag | Verfahren zur kontinuierlichen Wirbelschichtagglomeration |
| DE19514187C1 (de) * | 1995-04-21 | 1996-05-15 | Degussa | Verfahren und Vorrichtung zur Herstellung von Granulaten durch Wirbelschicht-Sprühgranulation |
| DE19520839A1 (de) * | 1995-06-08 | 1996-12-12 | Hoechst Schering Agrevo Gmbh | Herbizide Mittel mit 4-Iodo-2-[3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) ureidosulfonyl] -benzoesäureestern |
| DE19613395A1 (de) * | 1996-04-03 | 1997-10-09 | Basf Ag | Granulate hygroskopischer, wasserlöslicher Produkte |
| TW529910B (en) * | 1997-01-30 | 2003-05-01 | Basf Ag | Solid mixtures based on sulfonylureas and adjuvants |
| HU228225B1 (en) * | 1997-03-24 | 2013-02-28 | Basf Ag | Solid mixtures based on sulfonylurea and adjuvants |
| DE10036002A1 (de) * | 2000-07-25 | 2002-02-14 | Aventis Cropscience Gmbh | Herbizide Mittel |
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- 2004-02-11 BR BRPI0407639-7A patent/BRPI0407639A/pt not_active IP Right Cessation
- 2004-02-11 CN CNB2004800078871A patent/CN100333640C/zh not_active Expired - Fee Related
- 2004-02-11 CA CA002516416A patent/CA2516416A1/en not_active Abandoned
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101980600A (zh) * | 2008-02-05 | 2011-02-23 | 北美爱利思达生命科学有限责任公司 | 低熔点活性化合物的固体制剂 |
| CN103651341A (zh) * | 2013-12-27 | 2014-03-26 | 山东省农药科学研究院 | 含百草枯二氯化物的颗粒剂及其制备方法 |
| CN103766346A (zh) * | 2013-12-27 | 2014-05-07 | 山东省农药科学研究院 | 含百草枯二氯化物的水分散性颗粒剂及其制备方法 |
| CN103766346B (zh) * | 2013-12-27 | 2015-08-26 | 山东省农药科学研究院 | 含百草枯二氯化物的水分散性颗粒剂及其制备方法 |
| CN103651341B (zh) * | 2013-12-27 | 2016-06-15 | 山东省农药科学研究院 | 含百草枯二氯化物的颗粒剂及其制备方法 |
| CN116806821A (zh) * | 2023-06-27 | 2023-09-29 | 山东京博农化科技股份有限公司 | 一种包含高熔点原药和低熔点原药的水分散粒剂的加工方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006517935A (ja) | 2006-08-03 |
| DE10307078A1 (de) | 2004-09-09 |
| AU2004212689A1 (en) | 2004-09-02 |
| EA008142B1 (ru) | 2007-04-27 |
| MXPA05008870A (es) | 2005-11-16 |
| CA2516416A1 (en) | 2004-09-02 |
| CN100333640C (zh) | 2007-08-29 |
| WO2004073403A1 (de) | 2004-09-02 |
| US20060234863A1 (en) | 2006-10-19 |
| EP1596654A1 (de) | 2005-11-23 |
| EA200501300A1 (ru) | 2006-02-24 |
| BRPI0407639A (pt) | 2006-02-21 |
| ZA200506603B (en) | 2007-01-31 |
| KR20050102662A (ko) | 2005-10-26 |
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