CN105007723A - 用于改善水溶性除草剂盐和浓缩肥料的相容性的组合物和方法 - Google Patents
用于改善水溶性除草剂盐和浓缩肥料的相容性的组合物和方法 Download PDFInfo
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- CN105007723A CN105007723A CN201380063164.2A CN201380063164A CN105007723A CN 105007723 A CN105007723 A CN 105007723A CN 201380063164 A CN201380063164 A CN 201380063164A CN 105007723 A CN105007723 A CN 105007723A
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- Prior art keywords
- ammonium
- salt
- aqueous solution
- weed killer
- killer herbicide
- Prior art date
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- 239000004009 herbicide Substances 0.000 title claims abstract description 143
- 239000000203 mixture Substances 0.000 title claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 150000003839 salts Chemical class 0.000 title claims abstract description 82
- 239000003337 fertilizer Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 103
- 238000002425 crystallisation Methods 0.000 claims abstract description 62
- 230000008025 crystallization Effects 0.000 claims abstract description 62
- 239000003112 inhibitor Substances 0.000 claims abstract description 61
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 96
- 239000000243 solution Substances 0.000 claims description 73
- 239000007864 aqueous solution Substances 0.000 claims description 59
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims description 58
- -1 diethylaluminum ethoxide ammonium Chemical compound 0.000 claims description 52
- 239000002253 acid Substances 0.000 claims description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 42
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 39
- 239000012141 concentrate Substances 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 34
- 239000005562 Glyphosate Substances 0.000 claims description 33
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 33
- 229940097068 glyphosate Drugs 0.000 claims description 33
- 239000007921 spray Substances 0.000 claims description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 150000001767 cationic compounds Chemical class 0.000 claims description 21
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 21
- 125000004104 aryloxy group Chemical group 0.000 claims description 20
- 150000001768 cations Chemical class 0.000 claims description 19
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 19
- 230000006872 improvement Effects 0.000 claims description 17
- 238000007046 ethoxylation reaction Methods 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- WZEMSIKSCALWJZ-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO.CCO WZEMSIKSCALWJZ-UHFFFAOYSA-N 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- ZXVOCOLRQJZVBW-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO ZXVOCOLRQJZVBW-UHFFFAOYSA-N 0.000 claims description 10
- 229960001231 choline Drugs 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- JJWLVOIRVHMVIS-UHFFFAOYSA-O isopropylaminium Chemical compound CC(C)[NH3+] JJWLVOIRVHMVIS-UHFFFAOYSA-O 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 claims description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 claims description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 9
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005627 Triclopyr Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- REEQLXCGVXDJSQ-UHFFFAOYSA-N trichlopyr Chemical compound OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 0.000 claims description 7
- WNTGYJSOUMFZEP-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(Cl)C=C1C WNTGYJSOUMFZEP-UHFFFAOYSA-N 0.000 claims description 6
- LLWADFLAOKUBDR-UHFFFAOYSA-N 2-methyl-4-chlorophenoxybutyric acid Chemical compound CC1=CC(Cl)=CC=C1OCCCC(O)=O LLWADFLAOKUBDR-UHFFFAOYSA-N 0.000 claims description 6
- 239000005558 Fluroxypyr Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- MEFQWPUMEMWTJP-UHFFFAOYSA-N fluroxypyr Chemical compound NC1=C(Cl)C(F)=NC(OCC(O)=O)=C1Cl MEFQWPUMEMWTJP-UHFFFAOYSA-N 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 238000005574 benzylation reaction Methods 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 159000000011 group IA salts Chemical class 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 238000005887 phenylation reaction Methods 0.000 claims description 4
- YIVXMZJTEQBPQO-UHFFFAOYSA-N 2,4-DB Chemical compound OC(=O)CCCOC1=CC=C(Cl)C=C1Cl YIVXMZJTEQBPQO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002794 2,4-DB Substances 0.000 claims description 3
- MZHCENGPTKEIGP-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(Cl)C=C1Cl MZHCENGPTKEIGP-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005574 MCPA Substances 0.000 claims description 3
- 239000005575 MCPB Substances 0.000 claims description 3
- 101150039283 MCPB gene Proteins 0.000 claims description 3
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims 6
- 150000001875 compounds Chemical group 0.000 claims 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 3
- 238000009333 weeding Methods 0.000 claims 3
- 239000002585 base Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 239000013049 sediment Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 11
- 238000010790 dilution Methods 0.000 description 11
- 239000012895 dilution Substances 0.000 description 11
- 229920002125 Sokalan® Polymers 0.000 description 10
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 9
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229940043237 diethanolamine Drugs 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000003905 agrochemical Substances 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
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- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011785 micronutrient Substances 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 3
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- PMDFRWFAWDCIGH-UHFFFAOYSA-M O.O.O.O.O.O.[Fe+].S(=O)(=O)([O-])[O-].[NH4+] Chemical compound O.O.O.O.O.O.[Fe+].S(=O)(=O)([O-])[O-].[NH4+] PMDFRWFAWDCIGH-UHFFFAOYSA-M 0.000 description 3
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- 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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
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- 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
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
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Abstract
提供了用于改善包含至少一种除草活性物的水溶性盐的除草剂水溶液和高浓度肥料如硫酸铵的相容性的方法和组合物,包括添加特定的聚合物结晶抑制剂。
Description
发明领域
本发明通常涉及一类可用于改善含水溶性活性成分,例如2,4-滴(2,4-D)DMA(4-二氯苯氧基乙酸,二甲胺盐)的除草剂水溶液和肥料的相容性的新型聚合物结晶抑制剂。
发明背景
农药和植物生长调节化学品的含水浓缩物配制剂在世界范围内广泛用于农业、工业、娱乐和住宅区域中。该类浓缩物的活性成分通常包含酸官能基团如羧酸或膦酸,其更通常地呈其水溶性盐的形式。含水浓缩物基本上为活性成分以较高浓度于水中的溶液,其预期在通过喷雾或其他方式施用之前在水中稀释。在施用前,通常将含水浓缩物稀释于约10-约500倍于其自身体积的水中。
包含水溶性农药和植物生长调节活性成分如2,4-滴DMA的配制剂在稀释至肥料溶液中时可能经历不相容性。不相容性自身体现为快速形成沉淀物。本领域技术人员公知的是沉淀物的形成主要是由于具有无机离子的2,4-滴(4-二氯苯氧基乙酸)的有限溶解性所致。该沉淀物可堵塞施用设备的喷嘴中的筛网,这导致变形的喷雾模式。该变形的模式导致除草剂混合物施用期间的不良叶片覆盖,且可导致降低的功效。由于降低的水溶性可降低杂草对除草剂的吸收,因此不溶性沉淀物的形成本身可降低功效。肥料如硫酸铵的添加可恶化该不相容性。
目前市场上不存在避免在上述情况下形成沉淀物的令人满意的选项。存在一些使晶体生长最小化,从而使得农药“鸡尾酒”可在最小至无模式妨碍下施用的选项。已看出合成聚合物可在水溶性活性物与肥料混合时防止形成沉淀物。在更苛刻的情况下,聚合物可大大降低沉淀物的数量。
已看出根据本发明使用特定聚合物防止或大大抑制了水溶性除草剂与肥料混合时沉淀物的形成。
发明简述
本发明通常涉及一类可用于改善除草剂水溶液与肥料的相容性的新型聚合物结晶抑制剂。本发明还涉及一种改善除草剂水溶液与肥料溶液的相容性的方法,其中该类溶液包含一种或多种选自NH4 +、Na+、K+、Ca2+、Mg2+、Fe2+、Fe3+、Cu2+、Mn2+和Zn2+的无机阳离子,所述方法包括向除草剂水溶液中添加一种或多种本发明的聚合物结晶抑制剂。
此外,还提供了一种具有改善的相容性的除草剂水溶液,其包含至少一种芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐和/或草甘膦(glyphosate)的水溶性盐,和>16重量%的一种或多种肥料,和一种或多种结构I的聚合物结晶抑制剂。
此外,还提供了一种干除草剂组合物,其包含2,4-滴的水溶性盐和/或草甘膦的水溶性盐、>16重量%的一种或多种肥料和一种或多种结构I的聚合物结晶抑制剂。
附图简述
图1-12描述了各种实验结果。
发明详述
提供了包含至少一种芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐和草甘膦的水溶性盐以及任选>16重量%的一种或多种肥料的除草剂水溶液以及用于产生该溶液的方法。本文所述的除草剂水溶液相对于先前已知的包含所列组分的除草剂水溶液具有改善的相容性。本文所述的除草剂水溶液包含起相容性试剂作用的聚合物结晶抑制剂。当存在无机或有机铵阳离子时,所述聚合物结晶抑制剂是尤其有用的,且提供了相容性而无需提高所述溶液的pH值。
已知芳氧基链烷酸的水溶性盐如2,4-滴盐的水溶液可具有相容性问题,从而在酸当量(ae)浓度为约0.3重量%或更高,pH为约6或更低,且存在足够浓度的无机阳离子如K+、Na+、Ca2+、Mg2+、NH4 +、Fe2+、Fe3+等的条件下,导致形成沉淀的固体。由2,4-滴盐的这些溶液形成沉淀固体所需的精确条件还取决于所用水的温度和硬度、所述溶液中的各组分如肥料的实际组成和浓度。
将硫酸铵添加至包含草甘膦的含水除草剂喷雾混合物中以提高除草剂性能的通常实践也可导致相容性问题。例如,如果在其中添加有硫酸铵的含草甘膦的喷雾混合物中存在除草剂如2,4-滴二甲铵(DMA),则如果pH值和2,4-滴浓度处于本文所述的范围内,可能发生固体结晶。
提供了改善除草剂水溶液与一种或多种高浓度肥料的相容性的方法,包括向所述除草剂水溶液中添加一种或多种式I的聚合物结晶抑制剂。
其中A为:
其中R1、R2和R3独立地为H、CH3、COOH或CH2COOH,L为连接基团,包括—C(=O)—O—、—C(=O)—N—、—CH2—、—O—、—O—C(=O)—、尿烷、脲或直接键;且其中Rhy为疏水性结构部分,其为直链或支化烷基、环烷基、芳基、烷芳基或其烷氧基化衍生物。在式I中,x为A的摩尔%且为约5-80%,z为C的摩尔%且为约0-25%,其余为y摩尔%B,其为约1-95摩尔%。在式I聚合物结晶抑制剂的另一实施方案中,x为约10-70摩尔%A,z为约2-20摩尔%C,其余为y摩尔%B。在又一实施方案中,在式I的聚合物结晶抑制剂中,x为约15-50摩尔%A,z为约5-15摩尔%C,其余为y摩尔%B;在又一实施方案中,y为约80-35摩尔%B。
Rhy优选为芳族的且为萘、乙氧基化萘、苯基、乙氧基化苯基、苄基或乙氧基化苄基。最优选苯基或苄基。然而,Rhy可为脂族的或烷氧基化脂族的,例如直链或支化C1-C32基团。当Rhy为直链脂族的或烷氧基化直链脂族的时,其优选为甲基、乙基或丁基或其乙氧基化衍生物。Rhy优选为支化脂族的或者烷氧基化支化脂族的,且优选为2-乙基己基、2-丁基辛基、2-己基癸基、2-辛基十二烷基、2-癸基十四烷基、2-十二烷基十六烷基、异丙基、异丁基、叔丁基、叔辛基或其乙氧基化衍生物。最优选2-乙基己基。如果Rhy为直链的且大于C8,则优选为不饱和疏水物。这些不饱和疏水物可为油基、椰油基、大豆油基、瓢儿菜基(erucyl)或牛油。Rhy可通过聚合单体引入该分散剂聚合物中,例如但不限于苯乙烯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、乙氧基化苄基(甲基)丙烯酸酯、乙氧基化苯基(甲基)丙烯酸酯、甲基丙烯酸甲酯、丙烯酸甲酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-丁基辛酯、(甲基)丙烯酸2-己基癸酯、(甲基)丙烯酸2-辛基十二烷基酯、(甲基)丙烯酸2-癸基十四烷基酯、(甲基)丙烯酸2-十二烷基十六烷基酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、叔辛基丙烯酰胺、丙烯酸辛酯、丙烯酸月桂基酯、丙烯酸硬脂基酯、丙烯酸山萮基酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸辛酯、甲基丙烯酸月桂基酯、甲基丙烯酸硬脂基酯、甲基丙烯酸山萮基酯、2-乙基己基丙烯酰胺、辛基丙烯酰胺、月桂基丙烯酰胺、硬脂基丙烯酰胺、山萮基丙烯酰胺、丙烯酸丙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸己酯、乙酸乙烯基酯、1-烯丙基萘、2-烯丙基萘、1-乙烯基萘和2-乙烯基萘。
式I的聚合物结晶抑制剂通常通过共聚两种单体而制备,包括单体A和单体B,且任选包括单体C,这提供了式I中所示的部分A、B和C。式I的聚合物结晶抑制剂优选具有5-80摩尔%A和0-25摩尔%C,其余为B。式I的聚合物结晶抑制剂更优选具有10-70摩尔%A和2-20摩尔%C,其余为B。式I的聚合物结晶抑制剂最优选具有15-50摩尔%A和5-15摩尔%C,其余为B。
式I的组分B衍生自聚合单体B,其可为烯属不饱和羧酸单体和/或其盐。可用于制备式I聚合物结晶抑制剂的烯属不饱和羧化单体包括但不限于丙烯酸、甲基丙烯酸、乙基丙烯酸、α-氯丙烯酸、α-氰基丙烯酸、β-甲基丙烯酸(巴豆酸)、α-苯基丙烯酸、β-丙烯酰氧基丙酸、山梨酸、α-氯山梨酸、当归酸、肉桂酸、对氯肉桂酸、β-苯乙烯基丙烯酸(1-羧基-4-苯基-1,3-丁二烯)、衣康酸、马来酸、柠康酸、中康酸、戊烯二酸、乌头酸、富马酸、三羧基乙烯(tricarboxy ethylene)、粘康酸、2-丙烯酰氧基丙酸和马来酸。还可包括可形成羧酸结构部分的单体如马来酸酐或丙烯酰胺。还可使用烯属不饱和羧化单体的组合。在一个方面,所述烯属不饱和羧酸单体为丙烯酸、马来酸或甲基丙烯酸。
任选的组分C衍生自聚合单体C,其可为烯属不饱和磺酸单体或膦酸单体和/或其盐或任何其他可聚合单体。烯属不饱和磺酸单体或膦酸单体(单体C)及其盐包括但不限于2-丙烯酰胺基-2-甲基丙烷磺酸或其钠盐(AMPS)、2-甲基丙烯酰胺基-2-甲基-1-丙烷磺酸、3-甲基丙烯酰胺基-2-羟基丙烷磺酸、烯丙基磺酸、甲基烯丙基磺酸、2-羟基-3-(2-丙烯氧基)丙烷磺酸、2-甲基-2-丙烯-1-磺酸、丙烯酸3-磺基丙酯、甲基丙烯酸3-磺基丙酯、磺基甲基丙烯酰胺、磺基次甲基(methyline)丙烯酰胺、苯乙烯磺酸钠、1-烯丙氧基-2-羟基丙烷磺酸钠、烯丙氧基苯磺酸、乙烯基磺酸、甲基烯丙基磺酸钠、磺化苯乙烯、烯丙氧基苯磺酸、乙烯基膦酸等。式I的聚合物结晶抑制剂也可包括作为与式I聚合物相连的相应羧酸、磺酸和膦酸基团的无机碱性盐和有机胺盐。在特定情况下,例如在改善含水溶性2,4-滴盐的水溶液的相容性的情况下,与式I聚合物相连的相应羧酸、磺酸和膦酸基团的有机胺盐是有用的。呈其相应有机铵阳离子形式的有机胺可选自但不限于单甲铵、异丙铵、丁铵、二甲铵、二乙铵、三乙铵、单乙醇铵、二乙醇铵、二甲基乙铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲铵、四乙铵和N,N,N-三甲基乙醇铵(胆碱),和由二甲氨基丙胺(DMAPA;N,N-二甲基丙烷-1,3-二胺)和二亚乙基三胺(DETA;双(2-氨基乙基)胺)制成的阳离子,或其混合物。
式I的聚合物结晶抑制剂可通过本领域已知的方法制备,例如美国专利5,650,473中所公开的那些,其相关部分通过引用并入本文。式I的聚合物结晶抑制剂可为无规的、嵌段的、星形的或者任何其他结构。式I的聚合物结晶抑制剂可具有约1,000-约20,000的重均分子量,且可包括其衍生物,例如碱金属盐如羧酸钠、有机铵盐或磺化衍生物。合适的式I聚丙烯酸化物共聚物包括例如725、725-D、747和747-D,以及Armak 2092,其由Akzo Nobel Surface Chemistry LLC(芝加哥,伊利诺斯州)商购获得。可用于本文所公开的组合物和方法的式I聚合物结晶抑制剂的其他实例包括甲基丙烯酸苄酯和丙烯酸的共聚物,以及苯乙烯和丙烯酸的共聚物。
如本文所用的那样,本发明的农业水溶液包含水溶性活性物,且其要么包含肥料,要么稀释至肥料中和/或与肥料混合。术语“农业化学活性物”意指用于农业应用中的任何物质。这些包括但不限于除草剂、杀昆虫剂、杀真菌剂、生物杀伤剂、杀软体动物剂、杀藻剂、植物生长调节剂、驱虫药、灭鼠剂、杀线虫剂、杀螨剂、抗阿米巴药、杀原生动物剂、作物安全剂和助剂的配制剂。活性物的具体实例包括:
除草剂:包括三嗪类,如莠去津(atrazine){6-氯-N-乙基-N'-(I-甲基乙基)-1,3,5-三嗪-2,4-二胺和扑草净(prometryn){N,N'-双(1-甲基乙基)-6-(甲硫基)-1,3,5-三嗪)-2,4-二胺};取代的脲类,如敌草隆(diuron){N'-(3,4-二氯苯基)-N,N-二甲基脲};磺酰脲类,如精甲磺胺黄隆(metsulfuron-methyl){2-[[[[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基]羰基]氨基]磺酰基]苯甲酸酯}、醚苯黄隆(triasulfuron){2-(2-氯乙氧基)-N-[[(4-甲氧基-6-甲基-l,3,5-三嗪-2-基)氨基]羰基]苯磺酰胺}、苯黄隆(tribenuron-methyl){2-[[[[(4-甲氧基-6-甲基-I,3,5三嗪-2-基)甲氨基]羰基]氨基]磺酰基]苯甲酸甲酯}和绿黄隆(chlorsulfuron){2-氯-N-[[(4-甲氧基-6-甲基-1,3,5三嗪-2-基)氨基]羰基]苯磺酰胺};二氨基甲酸酯类,如苯敌草(phenmedipham){3-[(甲氧基羰基)氨基]苯基(3-甲基苯基)氨基甲酸酯};和
杀真菌剂:包括硫代氨基甲酸酯类,特别是亚烷基双(二硫代氨基甲酸酯)类,例如代森锰(maneb){[1,2-乙烷二基双[二硫代氨基甲酸](2-)]锰}和代森锰锌(mancozeb){[[1,2-乙烷二基双[二硫代氨基甲酸]](2-)]锰与[[1,2-乙烷二基双[二硫代氨基甲酸]](2-)]锌的混合物};嗜球果伞素类,如腈嘧菌酯(azoxystrobin){(E)-2-[[6-(2-氰基苯氧基)-4-嘧啶基]氧基]-a-(甲氧基亚甲基)苯乙酸甲酯}60和亚胺菌(kresoxim-methyl){(E)-a-(甲氧基亚氨基)-2-[(2-甲基苯氧基)甲基]苯乙酸甲酯};二羧酰亚胺类,如异丙定(iprodione){3-(3,5-二氯苯基)-N-异丙基-2,4-二氧代咪唑烷-1-甲酰胺};唑类,如丙环唑(propiconazole){1-[2-(2,4-二氯苯基)-4-65丙基-1,3-二氧戊环-2-基-甲基-lH-1,2,4-三唑}和戊唑醇(tebuconazole){(RS)-I-对氯苯基-4,4-二甲基-3-(IH1,2,4-三唑-1-基甲基)戊烷-3-醇};卤代邻苯二甲腈类,如百菌清(chlorthalonil){2,4,5,6-四氯-1,3-二氰基苯};和无机杀真菌剂,如氢氧化铜{Cu(OH)2};
杀昆虫剂:包括苯甲酰脲类,如氟脲杀(difiubenzuron){N-[[(4-氯苯基)氨基]羰基]-2,6-5二氟苯甲酰胺)};和氨基甲酸酯类,如甲萘威(carbaryl){I-萘基甲基氨基甲酸酯};
杀螨剂,包括:四嗪类,如四螨嗪(clofentezine){3,6-双(2-氯苯基)-1,2,4,5-四嗪}。
所述农业化学活性物可为水溶性的。在水溶性活性物中,非选择性除草剂,特别是N-(膦酰基甲基)甘氨酸类除草剂,如草甘膦和草硫膦(sulphosate){分别为N-膦酰基甲基甘氨酸的异丙氨基和三甲基锍盐},和氧膦基氨基酸类,如草铵膦(glufosinate){2-氨基-4-(羟甲基氧膦基)丁酸},特别是作为铵盐。该类水溶性活性物可用作水分散性颗粒中的唯一活性物,但更通常地,其与水不溶性或水不溶混性活性物组合用于多活性物配制剂中。
本文所用的肥料意指添加至土壤中以提供一种或多种植物生长所必需的植物营养的任何天然或合成来源的有机或无机物质(除石灰材料之外)。肥料通常以变化的比例提供:
·6种大量营养素:氮(N)、磷(P)、钾(K)、钙(Ca)、镁(Mg)和硫(S);
·7种微量营养素:硼(B)、氯(Cl)、铜(Cu)、铁(Fe)、锰(Mn)、钼(Mo)和锌(Zn)。
所述农业化学活性物通常以溶液(SL)形式提供,且所述配制剂可包含助剂、防冻剂、消泡剂、染料或其他使功效最大化或者美观效果所需的水溶性添加剂。当将活性物的SL稀释至水中并单独使用时,在施用期间通常不产生问题。当与肥料一起施用时,形成水不溶性沉淀物,从而在施用期间导致问题和/或降低功效。为了防止形成沉淀物和/或晶体,所述配制剂中必须包含添加剂或者将添加剂直接添加至喷雾介质中。
本文所述的芳氧基链烷酸的水溶性盐包括例如2,4-滴((2,4-二氯苯氧基)乙酸)、2,4-滴丁酸(2,4-DB)、2,4-滴丙酸(dichlorprop)、2甲4氯丙酸(mecoprop)、2甲4氯(MCPA)和2甲4氯丁酸(MCPB)。本文所述的吡啶氧基链烷酸包括例如定草酯(triclopyr)和氟草烟(fluroxypyr)。所述芳氧基链烷酸和吡啶氧基链烷酸的水溶性盐包括包含有机铵阳离子的那些,例如但不限于单甲铵、异丙铵、丁铵、二甲铵、二乙铵、三乙铵、单乙醇铵、二乙醇铵、二甲基乙铵、二乙醇铵、三乙醇铵、三异丙醇铵、四甲铵、四乙铵和N,N,N-三甲基乙醇铵(胆碱),和由二甲氨基丙胺(DMAPA;N,N-二甲基丙烷-1,3-二胺)和二亚乙基三胺(DETA;双(2-氨基乙基)胺)制成的阳离子,或其混合物。包含所述芳氧基链烷酸和吡啶氧基链烷酸的水溶性盐的水溶液可包括除草剂喷雾溶液或除草剂浓缩物。
本文所述的用于改善除草剂水溶液的相容性的方法和组合物还可与包含芳基-和/或杂芳基羧酸类除草剂如氯氨吡啶酸(aminopyralid)、二氯皮考啉酸(clopyralid)、麦草畏(dicamba)、毒莠定(picloram)等的水溶性盐的水溶液一起使用。
本文所述的草甘膦的水溶性盐包括其中阳离子选自钾、钠和铵,以及有机铵如异丙铵、二甲铵、三乙铵、单乙醇铵、二乙醇铵、三乙醇铵、胆碱等,和三甲基锍阳离子及其混合物的那些盐。
本文所述的无机阳离子为当以显著量或浓度存在时可导致芳氧基链烷酸或吡啶氧基链烷酸的水溶性盐的水溶液(任选包含草甘膦)变得不相容且形成固体的那些。这些无机阳离子包括例如碱金属阳离子,如钠和钾;碱土金属阳离子,如钙和镁;过渡金属阳离子,如锰、铜、锌和铁;和铵。包含2,4-滴和草甘膦的水溶性盐的水溶液在低于约pH 6.5的pH水平下在显著浓度的无机阳离子存在下倾向于比更高pH水平下的该类溶液更不相容。
本文所用的术语无机阳离子的“显著浓度”是指存在于含有至少一种除草剂、杀虫剂、植物生长调节剂、其混合物等的水溶性盐的水溶液中的无机阳离子的浓度,其在至少一种高浓度(即>16重量%的浓度)肥料的存在下,如果存在所述溶液的不相容性所必需的所有其他条件(例如芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐和/或草甘膦的水溶性盐的组成和浓度,以及水的温度、硬度和pH值),则会导致固体从所述溶液中沉淀。例如,在室温下在包含大于约0.8重量%2,4-滴DMA(基于酸当量(ae))且用硬度为342份/百万份(ppm)的水配制且pH值为约5的水溶液中,约0.8重量%(wt%,基于ae)的草甘膦钾盐浓度是不相容的。除本文所述的其他因素之外,该除草剂溶液的相容性取决于存在于所述溶液中的无机阳离子的总浓度和实际组成。
可将无机阳离子引入本文所述除草剂水溶液中的成分可包括但不限于包含肥料、微量营养素、硬水、辅助配制成分等,以及含无机阳离子如钾、钠和铵的草甘膦的水溶性盐的产品或水溶液。
本文所述的方法和组合物中可包括肥料,其可分散或溶于水中,且可包含其量足以导致与包含至少一种芳氧基链烷酸、吡啶氧基链烷酸和草甘膦的水溶性盐的水溶液混合时导致不相容性问题的无机阳离子,如铵和钾。可任选包括在本文所述方法和组合物中的肥料量大于或等于16重量%。可任选包括在本文所述方法和组合物中的肥料量的其他实例包括大于或等于17重量%、大于或等于18重量%、大于或等于19重量%、大于或等于20重量%、大于或等于21重量%、大于或等于22重量%、大于或等于23重量%、大于或等于24重量%、大于或等于25重量%、大于或等于26重量%、大于或等于27重量%、大于或等于28重量%、大于或等于29重量%、大于或等于30重量%、大于或等于31重量%、大于或等于32重量%、大于或等于33重量%、大于或等于34重量%或大于或等于35重量%或大于或等于38重量%或大于或等于40重量%或大于或等于45重量%或更高。肥料可包括但不限于硫酸铵(AMS)、磷酸铵、硝酸铵;硝酸铵和尿素的溶液(其在本领域通常称为28%N或UAN);硫代硫酸铵、硝酸钾、磷酸钾、氯化钾、碳酸钾等,及其混合物。除其肥料性质之外,AMS和UAN通常在草甘膦除草剂处理中用作喷雾助剂或水调节剂以提高生物学功效。因此,经常将AMS与草甘膦混合,本文所述的方法和组合物可用于改善在将这些溶液与含芳氧基链烷酸的水溶性盐和/或吡啶氧基链烷酸的水溶性盐的除草剂水溶液组合时的相容性。
可用于本文所述方法和组合物中的微量营养素可包括植物生长和健康所必需的一种或多种营养素,其仅需以极低的量且可尤其包含一种或多种无机阳离子,例如锰、铜、铁、钼和锌的阳离子。可将所述微量营养素添加至包含芳氧基链烷酸、吡啶氧基链烷酸和/或草甘膦的水溶性盐的除草剂喷雾水溶液中以经济地输送至作物。如果对这些除草剂喷雾水溶液存在上文所述的不相容性条件,则这些溶液可发生相容性问题。
可在本文所述的除草剂水溶液中,特别是在浓缩物和预混浓缩物中导致不相容性的有机铵阳离子包括单甲铵、异丙铵、丁铵、二甲铵、二乙铵、三乙铵、单乙醇铵、二乙醇铵、二甲基乙铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲铵、四乙铵和N,N,N-三甲基乙醇铵(胆碱),或其混合物。
可用于本文所述方法和组合物中的辅助配制成分包括包含无机阳离子的那些产品或成分,且可选自助剂、消泡剂、抗微生物剂、缓冲剂、腐蚀抑制剂、消泡剂、沉积剂、分散剂、染料、冰点降低剂、中和剂、渗透助剂、螯合剂、喷雾漂移控制剂、铺展剂、稳定剂、粘合剂、悬浮助剂、粘度调节添加剂、润湿剂等中的一种或多种。
本文所述的聚合物结晶抑制剂可用于改善包含至少一种除草剂的水溶性盐,包括但不限于芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐和/或草甘膦的水溶性盐的除草剂水溶液在高浓度肥料,即>16重量%的一种或多种肥料存在下在桶混物、浓缩物或预混浓缩物中的相容性。在含水喷雾桶混物中,式I的聚合物结晶抑制剂相对于具有改善的相容性的除草剂喷雾水溶液可占0.01-5重量%、0.01-4重量%、0.01-3重量%、0.01-2重量%、0.01-1重量%、0.05-2重量%、0.05-1重量%、0.05-0.5重量%、0.1-0.4重量%、0.15-0.3重量%或0.15-0.25重量%。在含水浓缩物和含水预混浓缩物中,式I的聚合物结晶抑制剂相对于具有改善的相容性的除草剂水溶液可占0.05-10重量%、0.05-8重量%、0.05-6重量%、0.1-5重量%、0.2-5重量%、0.3-5重量%、0.4-5重量%、0.5-5重量%、0.5-4重量%、0.5-3重量%、1-3重量%或1.5-2.5重量%。
在一些情况下,本文所述的聚合物结晶抑制剂可包含可导致或增加在溶液中导致不相容性的无机离子的浓度的无机离子。在该情况下,所选聚合物结晶抑制剂应能使总无机离子浓度在添加该聚合物结晶抑制剂后相容化。或者,可使用不含无机阳离子的式I聚合物结晶抑制剂,例如式I的聚丙烯酸化物共聚物,其中羧基呈酸或有机铵盐形式。该类不含无机阳离子的式I聚合物结晶抑制剂可特别地用于改善含水除草剂浓缩物和预混浓缩物在环境温度和亚环境温度条件下的储存稳定性。
并非意欲受限于理论,本文所述的聚合物结晶抑制剂据信通过防止或抑制固体结晶或沉淀而改善除草剂水溶液与肥料的相容性。所述聚合物结晶抑制剂在防止形成这些固体中的相对效力可通过在滴定分析程序中测量固体结晶的起始pH值(OSPOC)而评估。特定组合物的OSPOC可通过用强酸,例如硫酸滴定无机阳离子的芳氧基链烷酸盐或吡啶氧基链烷酸盐,例如2,4-滴钾盐的溶液,直至在特定pH值(OSPOC)下开始形成固体或晶体而测定。在使用本文所述的任何特定聚合物结晶抑制剂下观察到的OSPOC越低,则其在防止本文所述的除草剂水溶液结晶,因此改善其相容性方面就可能表现得更好。
或者,本文所述的聚合物结晶抑制剂在改善本文所述的除草剂水溶液的相容性中的相对效力可通过测量无机阳离子的芳氧基链烷酸盐或吡啶氧基链烷酸盐,例如2,4-滴钾盐在桶混溶液中的临界结晶浓度(CCC)而测定。特定组合物的CCC可通过制备所述组合物的饱和和过饱和溶液或混合物,然后测量残留在溶液中的芳氧基链烷酸浓度而测定。在使用特定聚合物结晶抑制剂下观察到的CCC越高,则其在防止本文所述的除草剂水溶液结晶,因此改善其相容性方面就可能表现得更好。
可使用本文所述的聚合物结晶抑制剂相容化的本文所述的除草剂水溶液包括浓缩物、预混浓缩物,和通过将该浓缩物或预混浓缩物稀释或者通过桶混喷雾溶液的多组分而制得的喷雾溶液。所述含水除草剂浓缩物或预混浓缩物可包括使用相对于总组合物为0.05重量%-10重量%、0.05-8重量%、0.05-6重量%、0.1-5重量%、0.2-5重量%、0.3-5重量%、0.4-5重量%、0.5-3重量%、1-3重量%或1.5-2.5重量%的一种或多种本文所述的聚合物结晶抑制剂,和约20-约60重量%(基于酸当量)至少一种芳氧基链烷酸(如2,4-滴)的水溶性盐、吡啶氧基链烷酸(如定草酯)的水溶性盐和草甘膦的水溶性盐,或者包含一种或多种这些盐的预混物。所述具有改善的相容性的含水除草剂浓缩物或预混浓缩物优选为包含溶于或分散于该浓缩物中的聚合物结晶抑制剂的溶液,其在用产品或溶液且在本文所述的通常倾向于导致不相容性的条件下稀释于水中时形成具有改善的相容性的除草剂喷雾溶液。所述具有改善的相容性的除草剂喷雾溶液也可通过在使用时桶混该喷雾溶液的各组分而制备。该喷雾溶液也可与产品或溶液且在本文所述的通常倾向于导致不相容性的条件下组合或用其稀释,从而形成具有改善的相容性的除草剂喷雾溶液。
本文所述的聚合物结晶抑制剂在包含2,4-滴的可溶性盐、草甘膦的可溶性盐和无机阳离子的喷雾水溶液中的使用提供了在低于约6.5的pH水平下具有改善的相容性的溶液。此外,改善的相容性可在低于约pH 5.5下提供。此外,改善的相容性可在低于约pH 5下提供。
包含草甘膦和2,4-滴的水溶性盐的相容性喷雾水溶液可通过将草甘膦和2,4-滴的盐的水溶性浓缩物添加至包含式I聚合物结晶抑制剂的水溶液中而制备。可任选在所述喷雾溶液中添加其他辅助配制成分,例如水溶性或水分散性成分,包括但不限于分散剂、润湿剂、喷雾漂移降低剂、肥料和消泡剂。
如本文所述,相容化的含水除草剂浓缩物为包含溶于或分散于浓缩物中的聚合物结晶抑制剂的溶液,其在用产品或溶液且在通常倾向于导致不相容性(也如本文所述)的条件下稀释于水中时形成具有改善的相容性的除草剂喷雾溶液。
在使用本文所述的方法和组合物制备相容性含水除草剂浓缩物的典型方法中,将一种或多种式I的聚合物结晶抑制剂、至少一种除草活性成分,例如2,4-滴和/或草甘膦之一的水溶性盐、肥料和任何其他成分与水一起混合,从而提供所述含水浓缩物。成分的添加顺序和混合条件可由本领域技术人员确定。
本文所述的方法和组合物还包括干除草剂组合物,其包含2,4-滴的水溶性盐和/或草甘膦的水溶性盐、其量为16%或更高的至少一种肥料,和一种或多种上文所述的结构I的聚合物结晶抑制剂。干除草剂组合物可包含0.05-10重量%、0.05-8重量%、0.05-6重量%、0.1-5重量%、0.2-5重量%、0.3-5重量%、0.4-5重量%、0.5-10重量%、0.5-5重量%、0.5-4重量%、0.5-3重量%、1-3重量%或1.5-2.5重量%的一种或多种式I的聚合物结晶抑制剂,和约20-约80重量%(基于酸当量)的2,4-滴的水溶性盐或草甘膦的水溶性盐,或者2,4-滴和草甘膦的水溶性盐的混合物。本文所述的干除草剂组合物在使用产品或溶液且在本文所述的通常倾向于导致不相容性的条件下溶于水中时形成具有改善的相容性的除草剂喷雾溶液。
在制备所述干除草剂组合物的典型方法中,将一种或多种聚合物结晶抑制剂、至少一种2,4-滴和草甘膦的水溶性盐和任选的任何其他成分一起在水中混合,从而提供含水浓缩物。成分的添加顺序和所用的混合条件可由本领域技术人员容易地确定。然后,可将所述含水浓缩物通过移除水而浓缩,然后干燥以提供所述干除草剂组合物,其也可通过干混本文所述的成分而制备。可将所述干组合物添加至包含产品或溶液且处于本文所述的通常倾向于导致不相容性的条件下的喷雾水溶液中,从而形成具有改善的相容性的除草剂喷雾溶液。通常已知的是,浓缩或干配制剂可在使用时以约10-约500倍稀释率稀释或溶于水中,这取决于农业实践。
本文所述的方法和组合物可用于控制不希望的植物生长。在该用途中,将除草有效量的所述具有改善的相容性的喷雾水溶液施用至土壤区域或者目标植物叶片以对不希望的杂草植物进行杀灭或提供合适的控制。
用于典型农业应用中的本文所述方法和组合物中所用活性成分的有效量通常取决于例如植物类型、植物的生长阶段、环境条件的苛刻性、待防治的杂草和施用条件。通常使需要防治的杂草植物与包含约0.01-约10重量%,优选约0.1-约5重量%除草剂有效成分(基于酸当量,相对于总喷雾水溶液)的除草剂喷雾水溶液接触。所述接触可以以任何有效的方式进行。例如,可用呈处于载体如水中的溶液形式的活性成分喷雾所述植物的任何暴露部分,例如叶片或茎。
本文所述的方法和组合物尤其可用于防治自然耐受或通过基因操作或通过突变和选择而变得耐受或抗喷雾溶液中所含的除草剂的作物中的杂草。例如,可对已变得耐受或抗草甘膦和自然耐受或抗2,4-滴或以遗传方式耐受或抗2,4-滴的玉米、小麦、稻、大豆、糖用甜菜、棉花、卡诺拉(canola)和其他作物进行处理。本发明的除草剂喷雾水溶液还在防治许多已变得抗草甘膦的杂草,如加拿大蓬(Conyza canadensis,ERICA)中有效。
任选地,本文所述的方法和组合物可额外包含一种或多种表面活性剂。所述表面活性剂可为阴离子性的、阳离子性的或非离子性的。典型的表面活性剂包括烷基硫酸盐,例如二乙醇铵月桂基硫酸盐;烷芳基磺酸盐,例如十二烷基苯磺酸钙;烷基和/或芳烷基苯酚-氧化烯加成产物,例如壬基酚-C18乙氧基化物;醇-氧化烯加成产物,例如十三烷醇-C16乙氧基化物;皂类,例如硬脂酸钠;烷基萘磺酸盐,例如二丁基萘磺酸钠;磺基琥珀酸盐的二烷基酯,例如二(2-乙基己基)磺基琥珀酸钠;山梨醇酯,例如油酸山梨醇酯;季胺,例如月桂基三甲基氯化铵;乙氧基化胺,例如乙氧基化的牛油胺;甜菜碱类表面活性剂,例如椰油酰胺基丙基甜菜碱;脂肪酸的聚乙二醇酯,例如聚乙二醇硬脂酸酯;氧化乙烯和氧化丙烯的嵌段共聚物;单-和二-烷基磷酸酯的盐;及其混合物。待使用的这些表面活性剂的量和组合可由本领域技术人员容易地确定。如上文对聚合物结晶抑制剂所述的那样,可有利地避免使用包含影响结晶的水平的无机离子,如Na+、K+或NH4 +的表面活性剂,从而保持所述组合物的预期物理稳定性。
除上文所述的具体方法和组合物之外,本文所述的方法和组合物也可包括含有一种或多种额外相容性成分的组合物。这些额外成分可包括例如一种或多种可溶于或分散于所述组合物中的农药或其他成分,其可选自杀螨剂、杀藻剂、拒食剂、杀鸟剂、杀菌剂、鸟驱避剂、化学绝育剂、落叶剂、干燥剂、消毒剂、杀真菌剂、除草剂安全剂、除草剂、昆虫引诱剂、杀昆虫剂、昆虫驱避剂、哺乳动物驱避剂、交配干扰剂、杀螺剂、植物激活剂、植物尺寸和结构调节剂、灭鼠剂、化学信息素、增效剂和杀病毒剂。这些组合物中还可包含提供功能可用性的任何其他成分,例如消泡剂、抗微生物剂、缓冲剂、腐蚀抑制剂、分散剂、染料、香料、冰点降低剂、中和剂、增味剂、渗透助剂、螯合剂、喷雾漂移控制剂、铺展剂、稳定剂、粘合剂、粘度调节添加剂等。
现在借助下文非限制性实施例阐述本发明。
实施例1:
将100g水、0.0172g硫酸亚铁铵六水合物和107g异丙醇的初始进料添加至玻璃反应器中。将所述反应器内容物加热至回流(约84℃)。在回流下,经3.5小时添加75.6g丙烯酸和46.8苯乙烯(30摩尔%)的混合物的连续加料。同时但经4小时添加溶于25g水中的4.9g过硫酸钠和17.5g 35%过氧化氢的溶液。同时经3小时15分钟添加3.1g溶于60g水中的3-巯基丙酸溶液。将反应温度在约85-88℃下保持1小时。添加少量ANTIFOAM 1400(0.12g)(获自Dow Chemical)以抑制在蒸馏期间产生的任何泡沫。通过共沸蒸馏从所述聚合物溶液中除去所述醇助溶剂。在蒸馏期间,将溶于50g水中的70g二乙醇胺混合物缓慢滴入所述反应器中。蒸出约160g水和异丙醇的混合物。所述聚合物溶液的最终固体为约40%。
实施例2:
将125g水、0.02g硫酸亚铁铵六水合物和325g异丙醇的初始进料添加至玻璃反应器中。将所述反应器内容物加热至回流(约84℃)。在回流下,经3小时添加151.2g丙烯酸和158.6甲基丙烯酸苄酯(30摩尔%)和30g异丙醇的混合物的连续加料。同时但经3.5小时添加溶于80g水中的9.3g过硫酸钠和27.5g 35%过氧化氢的溶液。同时经2小时45分钟添加3.5g溶于50g水中的3-巯基丙酸溶液。将反应温度在约85-88℃下保持1小时。添加少量ANTIFOAM 1400(0.1g)(获自Dow Chemical)以抑制在蒸馏期间产生的任何泡沫。通过共沸蒸馏从所述聚合物溶液中除去所述醇助溶剂。在蒸馏期间,将溶于200g水中的100g二乙醇胺混合物缓慢滴入所述反应器中。蒸出约460g水和异丙醇的混合物。将所得产物用400g水稀释,所述聚合物溶液的最终固体为约35%。
实施例3:
将100g水、0.0199g硫酸亚铁铵六水合物和175g异丙醇的初始进料添加至玻璃反应器中。将所述反应器内容物加热至回流(约84℃)。在回流下,经3.5小时添加32.4g丙烯酸和109.2苯乙烯(70摩尔%)的混合物的连续加料。同时但经4小时添加溶于25g水中的5.7g过硫酸钠和20.2g 35%过氧化氢的溶液。同时经3小时15分钟添加5.7g溶于60g水中的3-巯基丙酸溶液。将反应温度在约85-88℃下保持1小时。添加少量ANTIFOAM 1400(0.1g)(获自DowChemical)以抑制在蒸馏期间产生的任何泡沫。通过共沸蒸馏从所述聚合物溶液中除去所述醇助溶剂。在蒸馏期间,将溶于200g水中的32.4g 50%NaOH的混合物缓慢滴入所述反应器中。蒸出约260g水和异丙醇的混合物。所述聚合物溶液的最终固体为约35%。
可用于本发明中的其他聚合物可通过美国专利5,650,473所述的方法和实施例1-3详细描述的程序合成。这些聚合物详述于下表中:
1AA=丙烯酸;AMPS=2-丙烯酰胺基-2-甲基丙烷磺酸;BzMA=甲基丙烯酸苄酯;DEA=二乙醇胺;Na=钠;2-EHA=丙烯酸2-乙基己酯。
这些聚合物的应用详述于下文实施例中:
评价2,4-滴DMA(344g/L)加麦草畏DMA(120g/L)的混合物与30-0-0(尿素-硝酸铵)肥料的相容性。测试的稀释率为将5ml除草剂混合物稀释至95ml30-0-0中。所有测试均在室温下进行。在所述除草剂溶液中测试一系列聚合物,它们为:
·用NaOH调节至pH 6.5的Agrilan 789L。Agrilan 789L为丙烯酸、甲基丙烯酸苄酯(BzMA)和AMPS的共聚物,获自AkzoNobel SurfaceChemistry;
·Alcosperse 602N:聚丙烯酸,钠盐;
·实施例1:30摩尔%苯乙烯+70摩尔%AA,二乙醇胺盐;
·实施例2:30摩尔%甲基丙烯酸苄酯+70摩尔%AA,二乙醇胺盐;
·2398-81 A:用二乙醇胺调节至pH 5.8的Alcosperse 602酸。
当将10重量%Agrilan 789L和Alcosperse 602N添加至除草剂溶液中时,快速形成沉淀物。其最可能为2,4-滴的钠盐或部分钠盐。当将789L降至5重量%时,未形成沉淀物。在5重量%Alcosperse 602N下,仍形成沉淀物。这归因于与789L相比,602N中存在更高摩尔%的钠。由于在具有602N的浓缩物中存在沉淀物,未测试稀释液。在静置1小时后的结果示于图1-3中。在静置2小时后的结果示于图4和5中。
在1小时间隔后,在不添加聚合物的除草剂混合物中存在大浓度的晶体。
存在于包含实施例2聚合物的稀释液中的浊雾不是由于2,4-滴盐沉淀所致。其是由于所述聚合物的低溶解度所致。Alcosperse 602的二乙醇胺盐作为相容性试剂/结晶抑制剂的表现不好。这是由于所述聚合物中不存在疏水性单体所致。迄今为止,尚未有非疏水性改性的聚合物可被接受为所测试水溶性活性物的晶体抑制剂/相容性试剂。
在2小时后,肥料溶液中所存在的变化很小的变化或者无变化。
用2,4-滴DMA 480g/L SL重复了相同的研究。所测试的聚合物为:
·用NaOH调节至pH 6.5的Agrilan 789L。Alcosperse 729L:丙烯酸、苯乙烯和AMPS的共聚物,获自AkzoNobel Surface Chemistry;
·Alcosperse 602N:聚丙烯酸,钠盐;
·实施例1:30摩尔%苯乙烯+70摩尔%AA,二乙醇胺盐;
·实施例2:30摩尔%甲基丙烯酸苄酯+70摩尔%AA,二乙醇胺盐
·2398-81 A:用二乙醇胺调节至pH 5.8的Alcosperse 602酸;
·Aquatreat AR 545:在该聚合物中通过使用甲基丙烯酸疏水改性;
·Agrilan 700L:甲基丙烯酸、AMPS和丙烯酸2-乙基己酯的共聚物,获自AkzoNobel Surface Chemistry;
·实施例3:70摩尔%苯乙烯+30摩尔%AA,钠盐。
在于SL中的5重量%所述聚合物溶液下,无一肥料稀释液表现良好,因为全都存在大量的沉淀物。将所述聚合物溶液的浓度提高至10重量%。结果示于图6-8中。
所述480g/1 SL所需的高浓度聚合物在使用Agrilan 789L时导致沉淀。钠抗衡离子的浓度足够高以至于形成2,4-滴钠盐,或者部分钠盐,这导致了沉淀物的形成。
在实施例1的聚合物中存在痕量的沉淀物,但这是迄今为止在本研究中表现最好的聚合物。令人感兴趣的是,实施例1聚合物的表现要比实施例2聚合物要好得多。这是由于实施例1中所存在苯乙烯和存在于实施例2中的甲基丙烯酸苄酯的差异所致。另一个感兴趣的现象是实施例3的聚合物在所述480g/L SL中表现不好。这可能归因于两个因素:1)苯乙烯含量过高,为70重量%,或者2)抗衡离子的差异具有明显的影响。
包含Agrilan 700L和Aquatreat AR 545的试样在稀释后立即产生大量沉淀。
当稀释至肥料中时,所述聚合物在2,4-滴DMA 480 SL中的浓度为约0.175体积%。将浓度提高至0.25体积%,并直接添加至所述肥料中以测试桶混施用的潜力。结果示于图9-12中。
实施例1的聚合物表现良好。实施例1的稀释液中存在痕量的沉淀物,但显著低于其他聚合物。存在稍微提高聚合物浓度会消除沉淀的可能性。对实施例1聚合物的唯一担忧是所述聚合物具有较长的溶解时间。与此相反,实施例2的聚合物立即溶剂化。实施例1聚合物的溶解时间可通过在该聚合物中插入甲基丙烯酸苄酯而降低。另一对比是实施例1聚合物和729L之间的对比。729L由于AMPS而立即溶剂化,但作为晶体抑制剂/相容性试剂表现不良。由于AMPS而提高所述聚合物的溶解度会抑制吸收,因此会降低性能。
Claims (44)
1.一种改善包含至少一种除草活性物的水溶性盐的除草剂水溶液和浓缩肥料的相容性的方法,其中所述浓缩肥料包含>16重量%的一种或多种肥料,所述方法包括向所述除草剂水溶液中添加一种或多种结构I的聚合物结晶抑制剂:
其中A为:
其中R1、R2和R3独立地为H、CH3、COOH或CH2COOH;L为连接基团,包括—C(=O)—O—、—C(=O)—N—、—CH2—、—O—、—O—C(=O)—、尿烷、脲或直接键;Rhy为疏水性的且包括直链或支化烷基、环烷基、芳基、烷芳基或其烷氧基化衍生物;
B衍生自烯属不饱和羧酸单体和/或其盐的聚合;和
C为任选的且衍生自烯属不饱和磺酸单体或膦酸单体和/或其盐的聚合,x为A的摩尔%且为约5-80%,z为C的摩尔%且为约0-25%,且y为B的摩尔%,其为约1-95摩尔%。
2.根据权利要求1的方法,其中所述除草活性物为芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、草甘膦的水溶性盐,或其组合和/或混合物。
3.根据权利要求1的方法,其中所述芳氧基链烷酸为2,4-滴(2,4-D)、2,4-滴丁酸(2,4-DB)、2,4-滴丙酸(dichlorprop)、2甲4氯丙酸(mecoprop)、2甲4氯(MCPA)或2甲4氯丁酸(MCPB),所述吡啶氧基链烷酸为定草酯(triclopyr)或氟草烟(fluroxypyr)。
4.根据权利要求1的方法,其中Rhy为直链芳基结构部分。
5.根据权利要求1的方法,其中Rhy为萘基、乙氧基化萘基、苯基、乙氧基化苯基、苄基或乙氧基化苄基。
6.根据权利要求1的方法,其中所述一种或多种肥料为硫酸铵。
7.根据权利要求1的方法,进一步包含一种或多种选自NH4 +、Na+、K+、Ca2+、Mg2+、Fe2+、Fe3+、Cu2+、Mn2+和Zn2+的无机阳离子,或者一种或多种选自单甲铵、异丙铵、丁铵、二甲铵、二乙铵、三乙铵、单乙醇铵、二乙醇铵、二甲基乙铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲铵、四乙铵和N,N,N-三甲基乙醇铵(胆碱),和由二甲氨基丙胺和二亚乙基三胺制成的阳离子,或其混合物的有机铵阳离子。
8.根据权利要求1的方法,其中所述除草剂水溶液为浓缩物或预混浓缩物。
9.根据权利要求8的方法,其中所述除草剂水溶液为包含2,4-滴和/或草甘膦的水溶性盐的浓缩物。
10.根据权利要求1的方法,其中所述除草剂水溶液为喷雾溶液。
11.根据权利要求1的方法,其中所述聚合物结晶抑制剂为包含聚丙烯酸化物基团、聚甲基丙烯酸化物基团或聚马来酸化物基团或其混合物的共聚物。
12.根据权利要求11的方法,其中包含聚丙烯酸化物基团的共聚物包含衍生自丙烯酸酯单体和苯乙烯或取代苯乙烯单体的聚合的疏水改性的基团。
13.根据权利要求1的方法,其中所述聚合物结晶抑制剂呈盐形式。
14.根据权利要求13的方法,其中所述盐为有机胺盐或无机碱性盐。
15.根据权利要求13的方法,其中所述盐包含选自如下组的有机铵阳离子:单甲铵、异丙铵、丁铵、二甲铵、二乙铵、三乙铵、单乙醇铵、二乙醇铵、二甲基乙铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲铵、四乙铵和N,N,N-三甲基乙醇铵(胆碱),和由二甲氨基丙胺和二亚乙基三胺制成的阳离子,或其混合物。
16.根据权利要求1的方法,其中结构I的聚合物结晶抑制剂包含相对于该结构I的聚合物结晶抑制剂的总重量为5-80摩尔%的A和0-25摩尔%的C,其余为B。
17.一种具有改善的相容性的除草剂水溶液,其中所述水溶液包含一种或多种除草活性物的水溶性盐且处于浓缩肥料下,其中所述浓缩肥料包含基于该溶液的总重量为>16重量%的至少一种肥料,和一种或多种结构I的聚合物结晶抑制剂:
其中A为:
其中R1、R2和R3独立地为H、CH3、COOH或CH2COOH;L为连接基团,包括—C(=O)—O—、—C(=O)—N—、—CH2—、—O—、—O—C(=O)—或直接键;Rhy为疏水性的且包括直链或支化烷基、环烷基、芳基、烷芳基或其烷氧基化衍生物;
B衍生自烯属不饱和羧酸单体和/或其盐的聚合;和
C为任选的且衍生自烯属不饱和磺酸单体或膦酸单体和/或其盐的聚合,x为A的摩尔%且为约5-80%,z为C的摩尔%且为约0-25%,且y为B的摩尔%,其为约1-95摩尔%。
18.根据权利要求17的除草剂水溶液,其中所述水溶性除草剂为芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、草甘膦的水溶性盐,及其混合物和/或组合。
19.根据权利要求17的除草剂水溶液,其中所述芳氧基链烷酸为至少一种2,4-滴(2,4-D)、2,4-滴丁酸(2,4-DB)、2,4-滴丙酸(dichlorprop)、2甲4氯丙酸(mecoprop)、2甲4氯(MCPA)或2甲4氯丁酸(MCPB),所述吡啶氧基链烷酸为定草酯(triclopyr)或氟草烟(fluroxypyr)。
20.根据权利要求17的除草剂水溶液,其中Rhy为直链芳基结构部分。
21.根据权利要求17的除草剂水溶液,其中Rhy为萘基、乙氧基化萘基、苯基、乙氧基化苯基、苄基或乙氧基化苄基。
22.根据权利要求17的除草剂水溶液,其中所述一种或多种肥料为硫酸铵、磷酸铵、硝酸铵或其混合物。
23.根据权利要求17的除草剂水溶液,进一步包含一种或多种选自NH4 +、Na+、K+、Ca2+、Mg2+、Fe2+、Fe3+、Cu2+、Mn2+和Zn2+的无机阳离子,或者一种或多种选自单甲铵、异丙铵、丁铵、二甲铵、二乙铵、三乙铵、单乙醇铵、二乙醇铵、二甲基乙铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲铵、四乙铵、N,N,N-三甲基乙醇铵(胆碱),和由二甲氨基丙胺和二亚乙基三胺制成的阳离子,或其混合物的有机铵阳离子。
24.根据权利要求17的除草剂水溶液,其中所述聚合物结晶抑制剂呈盐形式。
25.根据权利要求24的除草剂水溶液,其中所述盐为有机胺盐或无机碱性盐。
26.根据权利要求24的除草剂水溶液,其中所述盐包含选自如下组的有机铵阳离子:单甲铵、异丙铵、丁铵、二甲铵、二乙铵、三乙铵、单乙醇铵、二乙醇铵、二甲基乙铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲铵、四乙铵、N,N,N-三甲基乙醇铵(胆碱),和由二甲氨基丙胺和二亚乙基三胺制成的阳离子,或其混合物。
27.根据权利要求17的除草剂水溶液,其为浓缩物或预混浓缩物。
28.根据权利要求27的除草剂水溶液,其中所述除草剂水溶液为包含2,4-滴和/或草甘膦的水溶性盐的浓缩物。
29.根据权利要求17的除草剂水溶液,其为喷雾溶液。
30.根据权利要求17的除草剂水溶液,其中所述聚合物结晶抑制剂为包含聚丙烯酸化物基团、聚甲基丙烯酸化物基团或聚马来酸化物基团或其混合物的共聚物。
31.根据权利要求30的除草剂水溶液,其中包含聚丙烯酸化物基团的共聚物包含衍生自丙烯酸酯单体和苯乙烯或取代苯乙烯单体的聚合的疏水改性的基团。
32.根据权利要求17的除草剂水溶液,其中结构I的聚合物结晶抑制剂包含相对于I的总重量为5-80摩尔%的A,0-25摩尔%的C,其余为B。
33.一种干除草剂组合物,其包含至少一种除草剂的水溶性盐,>16重量%的一种或多种肥料和一种或多种结构I的聚合物结晶抑制剂:
其中A为:
其中R1、R2和R3独立地为H、CH3、COOH或CH2COOH;L为连接基团,包括—C(=O)—O—、—C(=O)—N—、—CH2—、—O—、—O—C(=O)—或直接键;Rhy为疏水性的且包括直链或支化烷基、环烷基、芳基、烷芳基或其烷氧基化衍生物;
B衍生自烯属不饱和羧酸单体和/或其盐的聚合;和
C为任选的且衍生自烯属不饱和磺酸单体或膦酸单体和/或其盐的聚合,x为A的摩尔%且为约5-80%,z为C的摩尔%且为约0-25%,且y为B的摩尔%,其为约1-95摩尔%。
34.根据权利要求33的干除草剂组合物,其中所述除草剂为2,4-滴的水溶性盐和/或草甘膦的水溶性盐。
35.根据权利要求33的干除草剂组合物,其中Rhy为直链芳基结构部分。
36.根据权利要求33的干除草剂组合物,其中Rhy为萘基、乙氧基化萘基、苯基、乙氧基化苯基、苄基或乙氧基化苄基。
37.根据权利要求33的干除草剂组合物,其中所述一种或多种肥料为硫酸铵。
38.根据权利要求33的干除草剂组合物,进一步包含一种或多种选自NH4 +、Na+、K+、Ca2+、Mg2+、Fe2+、Fe3+、Cu2+、Mn2+和Zn2+的无机阳离子,或者一种或多种选自单甲铵、异丙铵、丁铵、二甲铵、二乙铵、三乙铵、单乙醇铵、二乙醇铵、二甲基乙铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲铵、四乙铵和N,N,N-三甲基乙醇铵(胆碱),和由二甲氨基丙胺和二亚乙基三胺制成的阳离子,或其混合物的有机铵阳离子。
39.根据权利要求33的干除草剂组合物,其中所述聚合物结晶抑制剂呈盐形式。
40.根据权利要求39的干除草剂组合物,其中所述盐为有机胺盐或无机碱性盐。
41.根据权利要求33的干除草剂组合物,其中所述盐包含选自如下组的有机铵阳离子:单甲铵、异丙铵、丁铵、二甲铵、二乙铵、三乙铵、单乙醇铵、二乙醇铵、二甲基乙铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲铵、四乙铵和N,N,N-三甲基乙醇铵(胆碱),和由二甲氨基丙胺和二亚乙基三胺制成的阳离子,或其混合物。
42.根据权利要求33的干除草剂组合物,其中所述聚合物结晶抑制剂为包含聚丙烯酸化物基团、聚甲基丙烯酸化物基团或聚马来酸化物基团或其混合物的共聚物。
43.根据权利要求42的干除草剂组合物,其中包含聚丙烯酸化物基团的共聚物包含衍生自丙烯酸酯单体和苯乙烯或取代苯乙烯单体的聚合的疏水改性的基团。
44.根据权利要求33的干除草剂组合物,其中结构I的聚合物结晶抑制剂包含相对于I的总重量为5-80摩尔%的A和0-25摩尔%的C,其余为B。
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PCT/EP2013/076803 WO2014095785A1 (en) | 2012-12-19 | 2013-12-17 | Compositions and methods for improving the compatibility of water soluble herbicides salts and concentrated fertilizer |
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AU2013313054B2 (en) * | 2012-09-04 | 2017-01-12 | Akzo Nobel Surface Chemistry Llc | Compositions and methods for improving the compatibility of water soluble herbicide salts |
DE102015213635A1 (de) * | 2015-07-20 | 2017-01-26 | Clariant International Ltd | Pflanzennährstoff-Suspensionen und deren Verwendung zum Düngen von Pflanzen |
US10590045B2 (en) | 2015-10-12 | 2020-03-17 | Hydrite Chemical Co. | Liquid fertilizer |
RU2619948C1 (ru) * | 2016-05-26 | 2017-05-22 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Соль N1, N1, N4, N4-тетраметил-2-бутин-1,4-диамина с N-фосфонометилглицином, проявляющая гербицидную активность и способ ее получения |
US11109591B2 (en) | 2017-04-24 | 2021-09-07 | Taminco Bvba | Single phase liquids of alkanolamine salts of dicamba |
US10011536B1 (en) * | 2017-09-20 | 2018-07-03 | King Saud University | Encapsulated sustained release urea fertilizer |
CN112822943A (zh) * | 2018-09-04 | 2021-05-18 | 维乌作物保护有限公司 | 农业制剂中的结晶抑制剂 |
AR119374A1 (es) * | 2019-07-11 | 2021-12-15 | Monsanto Technology Llc | Mezclas de herbicidas que contienen sales de aminas de herbicidas ácidos |
US11746294B2 (en) * | 2021-05-28 | 2023-09-05 | Chemtreat, Inc. | Corrosion control using organic filmers and passivators in systems for processing nitrogen-containing solutions |
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CA2672160C (en) * | 2006-12-06 | 2016-01-26 | Akzo Nobel N.V. | Compatibility agents for herbicidal formulations comprising 2,4-(dichlorophenoxy) acetic acid salts |
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US8486862B2 (en) * | 2010-08-24 | 2013-07-16 | Dow Agrosciences Llc | Compositions and methods for improving the compatibility of water soluble herbicide salts |
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