CN1725951A - 微乳剂 - Google Patents
微乳剂 Download PDFInfo
- Publication number
- CN1725951A CN1725951A CNA2003801063722A CN200380106372A CN1725951A CN 1725951 A CN1725951 A CN 1725951A CN A2003801063722 A CNA2003801063722 A CN A2003801063722A CN 200380106372 A CN200380106372 A CN 200380106372A CN 1725951 A CN1725951 A CN 1725951A
- Authority
- CN
- China
- Prior art keywords
- microemulsion
- methyl
- alkyl
- group
- acid
- 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.)
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- 239000004530 micro-emulsion Substances 0.000 title claims abstract description 53
- 239000012141 concentrate Substances 0.000 title abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- -1 alkyl ether sulfate Chemical class 0.000 claims description 110
- 230000002363 herbicidal effect Effects 0.000 claims description 67
- 239000000203 mixture Substances 0.000 claims description 49
- 230000000694 effects Effects 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000003905 agrochemical Substances 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012872 agrochemical composition Substances 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 12
- 230000001473 noxious effect Effects 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 9
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 229920000151 polyglycol Polymers 0.000 claims description 8
- 239000010695 polyglycol Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000012868 active agrochemical ingredient Substances 0.000 abstract description 5
- 239000003945 anionic surfactant Substances 0.000 abstract description 4
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 239000002736 nonionic surfactant Substances 0.000 abstract 1
- 239000004009 herbicide Substances 0.000 description 58
- 241000196324 Embryophyta Species 0.000 description 52
- 239000002585 base Substances 0.000 description 49
- 150000001875 compounds Chemical class 0.000 description 47
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 28
- 229910052760 oxygen Inorganic materials 0.000 description 27
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 26
- 239000001301 oxygen Substances 0.000 description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 23
- 239000000194 fatty acid Substances 0.000 description 23
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 235000014113 dietary fatty acids Nutrition 0.000 description 16
- 229930195729 fatty acid Natural products 0.000 description 16
- 229910052736 halogen Inorganic materials 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000013543 active substance Substances 0.000 description 13
- 235000013877 carbamide Nutrition 0.000 description 13
- 125000004494 ethyl ester group Chemical group 0.000 description 13
- 239000001294 propane Substances 0.000 description 13
- 159000000000 sodium salts Chemical class 0.000 description 13
- 125000002769 thiazolinyl group Chemical group 0.000 description 13
- 239000004202 carbamide Substances 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- 229940100389 Sulfonylurea Drugs 0.000 description 11
- 150000001335 aliphatic alkanes Chemical group 0.000 description 11
- 150000001721 carbon Chemical group 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 229940017219 methyl propionate Drugs 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 239000005594 Phenmedipham Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 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 9
- 150000003254 radicals Chemical class 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000005579 Metamitron Substances 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 8
- 125000002521 alkyl halide group Chemical group 0.000 description 8
- 125000000304 alkynyl group Chemical group 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- VHCNQEUWZYOAEV-UHFFFAOYSA-N metamitron Chemical compound O=C1N(N)C(C)=NN=C1C1=CC=CC=C1 VHCNQEUWZYOAEV-UHFFFAOYSA-N 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 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 description 7
- 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 7
- 239000005503 Desmedipham Substances 0.000 description 7
- 239000005512 Ethofumesate Substances 0.000 description 7
- 239000005584 Metsulfuron-methyl Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000003282 alkyl amino group Chemical group 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 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 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 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 7
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 240000007594 Oryza sativa Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 238000009333 weeding Methods 0.000 description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical compound OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000003666 Amidosulfuron Substances 0.000 description 5
- 235000016068 Berberis vulgaris Nutrition 0.000 description 5
- 241000335053 Beta vulgaris Species 0.000 description 5
- 244000025254 Cannabis sativa Species 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 244000082988 Secale cereale Species 0.000 description 5
- 235000007238 Secale cereale Nutrition 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 5
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- ICJSJAJWTWPSBD-UHFFFAOYSA-N cloquintocet Chemical class C1=CN=C2C(OCC(=O)O)=CC=C(Cl)C2=C1 ICJSJAJWTWPSBD-UHFFFAOYSA-N 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000003337 fertilizer Substances 0.000 description 5
- 244000037671 genetically modified crops Species 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 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 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000575 pesticide Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- WJJBIYLGJUVNJX-UHFFFAOYSA-N pyrimidine-2-sulfonamide Chemical compound NS(=O)(=O)C1=NC=CC=N1 WJJBIYLGJUVNJX-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IMEVJVISCHQJRM-UHFFFAOYSA-N triflusulfuron-methyl Chemical compound COC(=O)C1=CC=CC(C)=C1S(=O)(=O)NC(=O)NC1=NC(OCC(F)(F)F)=NC(N(C)C)=N1 IMEVJVISCHQJRM-UHFFFAOYSA-N 0.000 description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 description 5
- 239000008158 vegetable oil Substances 0.000 description 5
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 4
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 239000005472 Bensulfuron methyl Substances 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 4
- 244000068988 Glycine max Species 0.000 description 4
- 239000005562 Glyphosate Substances 0.000 description 4
- 240000005979 Hordeum vulgare Species 0.000 description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 description 4
- 239000005574 MCPA Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- 239000005586 Nicosulfuron Substances 0.000 description 4
- VXMNDQDDWDDKOQ-UHFFFAOYSA-N Pyrazosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N(N=CC=2C(O)=O)C)=N1 VXMNDQDDWDDKOQ-UHFFFAOYSA-N 0.000 description 4
- 239000005616 Rimsulfuron Substances 0.000 description 4
- 241000209140 Triticum Species 0.000 description 4
- 235000021307 Triticum Nutrition 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- HBCBJXOSTRIDAQ-UHFFFAOYSA-N [S].NC=O Chemical compound [S].NC=O HBCBJXOSTRIDAQ-UHFFFAOYSA-N 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 4
- XMQFTWRPUQYINF-UHFFFAOYSA-N bensulfuron-methyl Chemical group COC(=O)C1=CC=CC=C1CS(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 XMQFTWRPUQYINF-UHFFFAOYSA-N 0.000 description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000004665 fatty acids Chemical group 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- BACHBFVBHLGWSL-UHFFFAOYSA-N methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate Chemical group C1=CC(OC(C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-UHFFFAOYSA-N 0.000 description 4
- ZTYVMAQSHCZXLF-UHFFFAOYSA-N methyl 2-[[4,6-bis(difluoromethoxy)pyrimidin-2-yl]carbamoylsulfamoyl]benzoate Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(OC(F)F)=CC(OC(F)F)=N1 ZTYVMAQSHCZXLF-UHFFFAOYSA-N 0.000 description 4
- RSMUVYRMZCOLBH-UHFFFAOYSA-N metsulfuron methyl Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=NC(OC)=N1 RSMUVYRMZCOLBH-UHFFFAOYSA-N 0.000 description 4
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- MEFOUWRMVYJCQC-UHFFFAOYSA-N rimsulfuron Chemical compound CCS(=O)(=O)C1=CC=CN=C1S(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 MEFOUWRMVYJCQC-UHFFFAOYSA-N 0.000 description 4
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 3
- 244000075850 Avena orientalis Species 0.000 description 3
- 235000007319 Avena orientalis Nutrition 0.000 description 3
- 239000005489 Bromoxynil Substances 0.000 description 3
- WMLPCIHUFDKWJU-UHFFFAOYSA-N Cinosulfuron Chemical compound COCCOC1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(OC)=NC(OC)=N1 WMLPCIHUFDKWJU-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
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Classifications
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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
- 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
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- 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
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/20—N-Aryl derivatives thereof
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种微乳剂,其包含a)一种或多种农业化学活性成分,b)一种或多种非醇类有机溶剂,c)一种或多种阴离子表面活性剂,和d)一种或多种非离子表面活性剂。该微乳剂适用于作物保护。
Description
本发明涉及作物保护制剂领域。特别是,本发明涉及包含农业化学活性成分的微乳剂形式的液体制剂。
通常,用于作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固体或液体活性成分制剂使用。
液体制剂描述于,例如EP 0 261 492、EP 0 394 847、WO 95/17822、WO 98/31223、WO 89/03176、EP 0 357 149、WO 02/45507、GB 2 267825 A、WO 94/23578、EP 0 330 904、EP 0 533 057、EP 0 533 057、DE 36 24 910、WO 01/74785、EP 0 400 585和EP 0 118 579中。
本发明的目的是提供一种具有优良的化学和物理稳定性以及农业化学活性的经改良的作物保护制剂。
出入意外地,现已发现该目的可以通过本发明特定的微乳剂(MC)达到。
因此,本发明涉及一种微乳剂,其包含
a)一种或多种农业化学活性成分,
b)一种或多种非醇类有机溶剂,
c)一种或多种阴离子表面活性剂,和
d)一种或多种非离子表面活性剂。
此外,本发明的微乳剂可以视需要还包含作为其它组分的常规助剂和添加剂。
术语“微乳剂(MC)”应理解为指用水稀释形成微乳液的组合物,例如水包油微乳液或油包水微乳液。微乳液应理解为是一种热力学稳定并且乳化相的液滴大小通常为10-400nm,优选50-250nm的乳液。
通常,本发明的微乳剂包含如下量的组分a)、b)、c)和d),其中除非另有说明,此处和整个说明书中“重量%”指所述组分基于制剂总量的相对量:
组分a):0.001-50重量%,优选0.1-30重量%,尤其优选2-25重量%。
组分b):10-90重量%,优选20-85重量%,尤其优选25-80重量%。
组分c):0.1-25重量%,优选1-20重量%,尤其优选2-15重量%。
组分d):0.1-60重量%,优选1.5-45重量%,尤其优选2-40重量%。
适宜的农业化学活性成分a)为,例如除草剂、杀虫剂、杀真菌剂、安全剂和生长调节剂。优选的活性成分为除草剂,例如叶部作用的除草剂如ALS抑制剂(例如磺酰胺类如氟酮磺隆、丙苯磺隆(propoxycarbazone)或氨唑草酮,或磺酰脲类如叠磺隆、碘磺隆、酰嘧磺隆、甲酰氨磺隆),吡氟酰草胺、含溴苯腈或碘苯腈的产品,选自芳氧基苯氧基丙酸酯类的除草剂如精唑禾草灵乙酯,甜菜除草剂例如甜菜胺、甜菜宁、乙氧呋草黄或苯嗪草酮,草甘膦或草铵膦或其它选自HPPD抑制剂类的活性物质(例如异唑草酮、磺草酮、甲基磺草酮)。
本发明微乳剂中存在的除草剂实例为ALS抑制剂(乙酰乳酸合成酶抑制剂),或不同于ALS抑制剂的除草剂如氨基甲酸酯类、硫代氨基甲酸酯类、N-卤代乙酰苯胺类、经取代的苯氧基-、萘氧基-和苯氧基苯氧基羧酸衍生物和杂芳氧基苯氧基链烷羧酸衍生物例如喹啉基氧基-、喹喔啉基氧基-、吡啶基氧基-、苯并噁唑基氧基-和苯并噻唑基氧基苯氧基链烷羧酸酯,环己烷二酮衍生物、含磷除草剂例如草铵膦类或草甘膦类除草剂,以及S-(N-芳基-N-烷基氨甲酰基甲基)二硫代磷酸酯。
ALS抑制剂尤其为咪唑啉酮类、嘧啶基氧基吡啶羧酸衍生物、嘧啶基氧基苯甲酸衍生物、三唑嘧啶磺酰胺衍生物和磺酰胺类,优选磺酰脲类。
对于本发明而言,作为组分存在于本发明的微乳剂中的ALS抑制剂的活性成分,例如磺酰脲类应理解为不仅指中性化合物,而且还始终包括其与无机和/或有机抗衡离子形成盐。例如磺酰脲类可以形成例如-SO2-NH-基团的氢被农业上适合的阳离子取代的盐。这些盐为,例如金属盐,尤其是碱金属或碱土金属盐,尤其是钠盐和钾盐,或其它的铵盐或与有机胺的盐。同样地,可以通过加入酸和碱基如氨基和烷基氨基的反应形成盐。对此适宜的酸是强无机酸和有机酸,例如HCl、HBr、H2SO4或HNO3。
优选的ALS抑制剂来自磺酰脲类系列,例如嘧啶-或三嗪基氨基羰基[苯-、吡啶-、吡唑-、噻吩-和(烷基磺酰基)烷基氨基]磺酰胺。嘧啶环或三嗪环上优选的取代基是烷氧基、烷基、卤烷氧基、卤烷基、卤素或二甲基氨基,所有的取代基可彼此独立地组合。苯、吡啶、吡唑、噻吩或(烷基磺酰基)烷基氨基部分的优选取代基为烷基、烷氧基、卤素如F、Cl、Br或I,氨基、烷基氨基、二烷基氨基、酰氨基如甲酰氨基、硝基、烷氧羰基、氨基羰基、烷基氨基羰基、二烷基氨基羰基、烷氧氨基羰基、卤烷氧基、卤烷基、烷基羰基、烷氧烷基、烷基磺酰基氨基烷基、(链烷基磺酰基)烷基氨基。这类适宜的磺酰脲类的实例为
A1)苯基-和苄基磺酰脲类以及相关的化合物,例如
1-(2-氯苯基磺酰基)-3-(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)脲(氯磺隆),
1-(2-乙氧基羰基苯基磺酰基)-3-(4-氯-6-甲氧基嘧啶-2-基)脲(氯嘧磺隆),
1-(2-甲氧基苯基磺酰脲)-3-(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)脲(甲磺隆),
1-(2-氯乙氧基苯基磺酰基)-3-(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)脲(醚苯磺隆),
1-(2-甲氧基羰基苯基磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲(sulfumeturon-methyl),
1-(2-甲氧基羰基苯基磺酰基)-3-(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)-3-甲基脲(苯磺隆),
1-(2-甲氧基羰基苄基磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲(苄嘧磺隆),
1-(2-甲氧基羰基苯基磺酰基)-3-(4,6-二(二氟甲氧基)嘧啶-2-基)脲,(氟嘧磺隆),
3-(4-乙基-6-甲氧基-1,3,5-三嗪-2-基)-1-(2,3-二氢-1,1-二氧代-2-甲基苯并-[b]噻吩-7-磺酰基)脲(EP-A 0 796 83),
3-(4-乙氧基-6-乙基-1,3,5-三嗪-2-基)-1-(2,3-二氢-1,1-二氧代-2-甲基苯并[b]-噻吩-7-磺酰基)脲(EP-A 0 079 683),
3-(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)-1-(2-甲氧基羰基-5-碘代苯基-磺酰基)脲(碘甲磺隆及其盐如钠盐,WO 92/13845),
DPX-66037,氟胺磺隆(参见Brighton Crop Prot.Conf.-Weeds-1995,853页),
CGA-277476,(参见Brighton Crop Prot.Conf.-Weeds-1995,79页),
2-[3-(4,6-二甲氧基嘧啶-2-基)脲基磺酰基]-4-甲磺酰胺甲基苯甲酸甲酯(mesosulfuron-methyl及其盐如钠盐,WO 95/10507),
N,N-二甲基-2-[3-(4,6-二甲氧基嘧啶-2-基)脲基磺酰基]-4-甲酰基氨基-苯甲酰胺(甲酰氨磺隆及其盐如钠盐,WO 95/01344);
A2)噻吩基磺酰脲类,例如
1-(2-甲氧基羰基噻吩-3-基)-3-(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)脲(噻吩磺隆);
A3)吡唑基磺酰脲类,例如
1-(4-乙氧基羰基-1-甲基吡唑-5-基-磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲(吡嘧磺隆);
3-氯-5-(4,6-二甲氧基嘧啶-2-基氨甲酰基氨磺酰基)-1-甲基-吡唑-4-羧酸甲酯(EP-A 0 282 613);
5-(4,6-二甲基嘧啶-2-基氨甲酰基氨磺酰基)-1-(2-吡啶基)吡唑基-4-羧酸甲酯(NC-330,参见Brighton Crop Prot.Conference‘Weeds’1991,Vol.1,45页及其后),
DPX-A8947,四唑嘧磺隆,(参见Brighton Crop Prot.Conf.‘Weeds’1995,65页);
A4)磺二酰胺衍生物类,例如
3-(4,6-二甲氧基嘧啶-2-基)-1-(N-甲基-N-甲基磺酰基氨基磺酰基)脲(酰嘧磺隆)及其结构类似物(EP-A 0 131 258和Z.Pfl.Krankh.Pfl.Schutz,Sonderheft XII,489-497(1990));
A5)吡啶基磺酰脲类,例如
1-(3-N,N-二甲基氨基羰基吡啶-2-基磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲(烟嘧磺隆),
1-(3-乙基磺酰基吡啶-2-基磺酰基)-3-(-(4,6-二甲氧基嘧啶-2-基)脲(砜嘧磺隆),
2-[3-(4,6-二甲氧基嘧啶-2-基)脲基磺酰基]-6-三氟甲基-3-吡啶基羧酸甲酯,钠盐(DPX-KE 459,氟啶磺隆,参见Brighton CropProt.Conf.Weeds,1995,49页),三氟啶磺隆及其钠盐;
A6)烷氧基苯氧基磺酰脲类,例如EP-A 0 342 569中所描述的,优选3-(4,6-二甲氧基嘧啶-2-基)-1-(2-乙氧基苯氧基)磺酰脲(乙氧嘧磺隆)或其盐;
A7)咪唑基磺酰脲类,例如
MON 37500、磺酰磺隆(参见Brighton Crop Prot.Conf.‘Weeds’,1995,57页),以及其它相关的磺酰脲衍生物及其混合物。
这些活性物质的典型代表尤其是下列化合物及其盐:
酰嘧磺隆、四唑嘧磺隆、苄嘧磺隆、氯嘧磺隆、氯磺隆、醚磺隆、环丙嘧磺隆、胺苯磺隆、乙氧嘧磺隆、啶嘧磺隆、氟啶嘧磺隆甲酯的钠盐、氟吡嘧磺隆、咪唑磺隆、甲磺隆、烟嘧磺隆、环氧嘧磺隆、氟嘧磺隆、氟磺隆、吡嘧磺隆、砜嘧磺隆、甲嘧磺隆、磺酰磺隆、噻吩磺隆、醚苯磺隆、苯磺隆、三氟啶磺隆及其钠盐、氟胺磺隆、碘甲磺隆及其钠盐(WO 92/13845)、叠磺隆及其钠盐(Agrow Nr.347,2000年3月,第22页(PJB Publications Ltd.2000)),以及甲酰氨磺隆及其钠盐(Agrow Nr.338,1999年10月15日,第26页(PJBPublications Ltd.1999))。
上述活性物质是已知的,例如描述于“The Pesticide Manual”(农药手册),第十二版(2000),The British Crop ProtectionCouncil(布赖顿作物保护会议)中,或具体活性物质后面所列的文献中。
其它适宜的ALS抑制剂实例为
B)咪唑啉酮类,例如
2-(4-异丙基-4-甲基-5-氧代-2-咪唑啉-2-基)-5-甲基苯甲酸甲酯和2-(4-异丙基-4-甲基-5-氧代-2-咪唑啉-2-基)-4-甲基苯甲酸(咪草酸),
5-乙基-2-(4-异丙基-4-甲基-5-氧代-2-咪唑啉-2-基)-吡啶-3-羧酸(咪唑乙烟酸),
2-(4-异丙基-4-甲基-5-氧代-2-咪唑啉-2-基)-喹啉-3-羧酸(咪唑喹啉酸),
2-(4-异丙基-4-甲基-5-氧代-2-咪唑啉-2-基)-吡啶-3-羧酸(咪唑烟酸),
5-甲基-2-(4-异丙基-4-甲基-5-氧代-2-咪唑啉-2-基)-吡啶-3-羧酸(imazethamethapyr);
C)三唑嘧啶磺酰胺衍生物类,例如
N-(2,6-二氟苯基)-7-甲基-1,2,4-三唑[1,5-c]嘧啶-2-磺酰胺(唑嘧磺草胺),
N-(2,6-二氯-3-甲基苯基)-5,7-二甲氧基-1,2,4-三唑[1,5-c]嘧啶-2-磺酰胺,
N-(2,6-二氟苯基)-7-氟-5-甲氧基-1,2,4-三唑[1,5-c]嘧啶-2-磺酰胺,
N-(2,6-二氯-3-甲基苯基)-7-氯-5-甲氧基-1,2,4-三唑[1,5-c]嘧啶-2-磺酰胺,
N-(2-氯-6-甲氧基羰基)-5,7-二甲基-1,2,4-三唑[1,5-c]嘧啶-2-磺酰胺(EP-A 0 343 752,US-A 4,988,812);
D)嘧啶基氧基吡啶羧酸和嘧啶基氧基苯甲酸衍生物,例如
3-(4,6-二甲氧基嘧啶-2-基)-氧基吡啶-2-羧酸苄酯(EP-A 0 249707),
3-(4,6-二甲氧基嘧啶-2-基)-氧基吡啶-2-羧酸甲酯(EP-A 0 249707),
2,6-二[(4,6-二甲氧基嘧啶-2-基)氧基]-苯甲酸(EP-A 0 321846),
2,6-二[(4,6-二甲氧基嘧啶-2-基)氧基]苯甲酸-1-(乙氧基羰基氧基乙基)酯(EP-A 0 472 113)。
不同于ALS抑制剂并且存在于本发明微乳剂中的除草活性物质为例如选自下组的除草剂:氨基甲酸酯、硫代氨基甲酸酯、N-卤代乙酰苯胺、经取代的苯氧基-、萘氧基-和苯氧基苯氧基羧酸衍生物、以及杂芳氧基苯氧基链烷基羧酸衍生物如喹啉基氧基-、喹喔啉基氧基-、吡啶基氧基-、苯并噁唑基氧基-和苯并噻唑基氧基苯氧基链烷基羧酸酯、环己烷二酮衍生物、含磷除草剂如草铵膦类和草甘膦类,以及S-(N-芳基-N-烷基氨甲酰基甲基)-二硫代磷酸酯。本发明优选的是苯氧基苯氧基-和杂芳氧基苯氧基羧酸酯及其盐,以及除草剂如灭草松、氰草津、莠去津、麦草畏或羟基苯腈如溴苯腈和碘苯腈及其盐,以及其它叶部作用的除草剂。
不同于ALS抑制剂并且可作为组分存在于本发明微乳剂中的适宜除草活性物质实例为:
E)苯氧基苯氧基-和杂芳氧基苯氧基羧酸衍生物类除草剂,例如
E1)苯氧基苯氧基-和苄氧基苯氧基羧酸衍生物,例如
2-(4-(2,4-二氯苯氧基)苯氧基)丙酸甲酯(禾草灵),
2-(4-(4-溴-2-氯苯氧基)苯氧基)丙酸甲酯(DE-A 26 01 548),
2-(4-(4-溴-2-氟苯氧基)苯氧基)丙酸甲酯(US-A 4,808,750),
2-(4-(2-氯-4-三氟甲基苯氧基)苯氧基)丙酸甲酯(DE-A 24 33067),
2-(4-(2-氟-4-三氟甲基苯氧基)苯氧基)丙酸甲酯(US-A4,808,750),
2-(4-(2,4-二氯苄基)苯氧基)丙酸甲酯(DE-A 24 17 487),
4-(4-(4-三氟甲基苯氧基)苯氧基)戊-2-烯乙酯,
2-(4-(4-三氟甲基苯氧基)苯氧基)丙酸甲酯(DE-A 24 33 067);
E2)“单核”杂芳氧基苯氧基链烷基羧酸衍生物,例如
2-(4-(3,5-二氯吡啶基-2-氧基)苯氧基)丙酸乙酯(EP-A 0 002925),
2-(4-(3,5-二氯吡啶基-2-氧基)苯氧基)丙酸炔丙酯(EP-A 0 003114),
2-(4-(3-氯-5-三氟甲基-2-吡啶基氧基)苯氧基)丙酸甲酯(EP-A0 003 890),
2-(4-(3-氯-5-三氟甲基-2-吡啶基氧基)苯氧基)丙酸乙酯(EP-A0 003 890),
2-(4-(5-氯-3-氟-2-吡啶基氧基)苯氧基)丙酸炔丙酯(EP-A 0191 736),
2-(4-(5-三氟甲基-2-吡啶基氧基)苯氧基)丙酸丁酯(吡氟禾草灵);
E3)“双核”杂芳氧基苯氧基链烷基羧酸衍生物,例如
2-(4-(6-氯-2-喹喔啉基氧基)苯氧基)丙酸甲酯和乙酯(喹禾灵甲酯和喹禾灵乙酯),
2-(4-(6-氟-2-喹喔啉基氧基)苯氧基)丙酸甲酯(参见J.Pest.Sci.Vol.10,61(1985)),
2-(4-(6-氯-2-喹喔啉基氧基)苯氧基)丙酸-2-异亚丙基氨基氧基乙酯(草酸),
2-(4-(6-氯苯并噁唑-2-基氧基)苯氧基)丙酸乙酯(噁唑禾草灵乙酯),其D(+)异构体(精唑禾草灵乙酯)和2-(4-(6-氯苯并噻唑-2-基氧基)苯氧基)丙酸乙酯(DE-A 26 40 730),
2-(4-(6-氯喹喔啉基氧基)苯氧基)丙酸四氢-2-呋喃基甲酯(EP-A 0 323 727);
F)N-氯乙酰苯胺类,例如
N-甲氧基甲基-2,6-二乙基-氯乙酰苯胺(甲草胺),
N-(3-甲氧基丙-2-基)-2-甲基-6-乙基-氯乙酰苯胺(异丙甲草胺),
2,6-二甲基N-(3-甲基-1,2,4-噁二唑-5-基甲基)-氯乙酰苯胺,
N-(2,6-二甲基苯基)-N-(1-吡唑基甲基)-氯乙酰苯胺(吡唑草胺);
G)硫代氨基甲酸酯,例如
S-乙基-N,N-二丙基硫代氨基甲酸酯(EPTC),
S-乙基-N,N-二异丁基硫代氨基甲酸酯(丁草敌);
H)环己烷二酮肟类,例如
3-(1-烯丙氧基亚氨基丁基)-4-羟基-6,6-二甲基-2-氧代环己-3-烯羧酸甲酯,(禾草灭),
2-(1-乙氧基亚氨基丁基)-5-(2-乙基硫代丙基)-3-羟基环己-2-烯-1-酮(烯禾啶),
2-(1-乙氧基亚氨基丙基)-5-(2-苯基硫代丙基)-3-羟基环己-2-烯-1-酮(环己烯草酮),
2-(1-(3-氯烯丙氧基)亚氨基丁基)-5-(2-乙基硫代丙基)-3-羟基环己-2-烯-1-酮,
2-(1-(3-氯烯丙氧基)亚氨基丙基)-5-(2-乙基硫代丙基)-3-羟基环己-2-烯-1-酮(烯草酮),
2-(1-乙氧基亚氨基丁基)-3-羟基-5-(噻喃-3-基)环己-2-烯酮(噻草酮),
2-(1-乙氧基亚氨基丙基)-5-(2,4,6-三甲基苯基)-3-羟基环己-2-烯-1-酮(三甲苯草酮);
I)苯甲酰基环己烷二酮类,例如
2-(2-氯-4-甲基磺酰基苯甲酰基)环己烷-1,3-二酮(SC-0051,EP-A 0 137 963),2-(2-硝基苯甲酰基)-4,4-二甲基环己烷-1,3-二酮(EP-A 0 274 634),2-(2-硝基-4-甲基磺酰基苯甲酰基)-4,4-二甲基环己-1,3-二酮(WO 91/13548,甲基磺草酮);
J)S-(N-芳基-N-烷基氨甲酰基甲基)二硫代膦酸酯如S-[N-(4-氯苯基)-N-异丙基氨甲酰基甲基]-O,O-二甲基二硫代磷酸酯(莎稗磷)。
K)烷基氮杂苯类,例如描述于WO-A 97/08156、WO-A-97/31904、DE-A-19826670、WO-A-98/15536、WO-A-8/15537、WO-A-98/15538、WO-A-98/15539,以及DE-A-19828519、WO-A-98/34925、WO-A-98/42684、WO-A-99/18100、WO-A-99/19309、WO-A-99/37627和WO-A-99/65882中的化合物,优选式(I)化合物
其中
RX为(C1-C4)-烷基或(C1-C4)-卤烷基;
RY为(C1-C4)-烷基、(C3-C6)-环烷基或(C3-C6)-环烷基-(C1-C4)-烷基,并且
A为-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-O-、-CH2-CH2-O-、-CH2-CH2-CH2-O-,
尤其优选式I1-I7的化合物
L)含磷除草剂,例如草铵膦类,如狭义的草铵膦,即D,L-2-氨基-4-[羟基(甲基)氧膦基]-丁酸、草铵膦单铵盐、L-草铵膦、L-或(2S)-2-氨基-4-[羟基(甲基)氧膦基]-丁酸、L-草铵膦单铵盐,或双丙氨膦(或双丙氨酰膦),即L-2-氨基-4-[羟基(甲基)氧膦基]丁酰基-L-丙氨酰-L-丙氨酸,尤其是其钠盐,或草甘膦类,例如草甘膦,即N-(膦酰甲基)甘氨酸、草甘膦单异丙基铵盐,草甘膦钠盐,或草硫膦(sulfosate),即N-(膦酰甲基)甘氨酸三甲基锍盐=N-(膦酰甲基)甘氨酸三甲基氧化锍盐。
组B至L的除草剂是已知的,例如公开于上述公开文本和下列文献中:“The Pesticide Manual”(农药手册),第12版,2000,TheBritish Crop Protection Council,以及“Agricultural ChemicalsBook II-Herbicides-”(农用化学品手册II-除草剂-),W.T.Thompson,Thompson Publications,Fresno CA,USA 1990和“Farm Chemicals Handbook’90”,Meister出版公司,Willoughby OH,USA,1990。
优选包含于本发明微乳剂中的农业化学活性物质a)为:
乙草胺(acetochlor)、苯草醚(aclonifen)、甲草胺(alachlor)、酰甲草胺(amidochlor)、酰嘧磺隆(amidosulfuron)、苄嘧磺隆(bensulfuron-methyl)、溴苯腈辛酸酯(bromoxynil octanoate)、丁草胺(butachlor)、氯磺隆(chlorsulfuron)、醚磺隆(cinosulfuron)、炔草酯(clodinafop-propargyl)、氯氰菊酯(cypermethrin)、2,4-D酯、2,4-DB酯、2,4-DP酯、CMPP酯、MCPA酯、溴氰菊酯(deltamethrin)、甜菜安(desmedipham)、禾草灵(diclofop-methyl)、吡氟酰草胺(diflufenican)、乙氧呋草黄(ethofumesate)、fenxoapropethyl、氟虫腈(fipronil)、乙羧氟草醚(fluoroglycofen)、甲酰氨磺隆(foramsulfuron)、咪唑烟酸(imazapyr)、咪唑磺隆(imazosulfuron)、碘甲磺隆(iodosulfuron-methyl)、imidocloprid、碘苯腈辛酸酯(ioxyniloctanoate)、异噁唑草酮(isoxaflutol)、乳氟禾草灵(lactofen)、叠磺隆(mesosulfuron-methyl)、异丙甲草胺(metolachlor)、甲磺隆(metsulfuron-methyl)、苯嗪草酮(metamitron)、烟嘧磺隆(nicosulfuron)、乙氧氟草醚(oxyfluorfen)、二甲戊乐灵(pendimethalin)、甜菜宁(phenmedipham)、氟嘧磺隆(primisulfuron-methyl)、噁草酸(propaquizafop)、吡嘧磺隆(pyrazosulfuron-methyl)、砜嘧磺隆(rimsulfuron)、氟胺磺隆(triflusulfuron-methyl)、氟乐灵(trifluralin)、碘磺隆(iodosulfuron)、咪鲜胺(prochloraz)、双甲脒(amitraz)、噁嗪酮(oxazinone)、丙炔噁草酮(oxadiargyl)、苯嗪草酮(metamitron)、mefenpyrdiethyl、甜菜宁(phenmedipham)、甜菜安(desmedipham)、双苯噁唑酸(isoxadifen-ethyl),及其盐类如钠盐。
适宜的非醇类有机溶剂b)为不包含醇基团的溶剂,例如烃类、羧酸衍生物、磷酸酯类、醚类、酮类或亚砜类如二甲亚砜。
烃类实例(参见,例如Rmpp Lexikon Chemie[Rmpp Dictionaryof Chemistry],第10版,第3卷,第2202页(1997),Georg ThiemeVerlag Stuttgart/New York)优选为在标准条件下是液体的化合物。该烃类可以为无环(脂肪族)烃或者环烃例如芳族或脂环族(环状脂肪族)烃。
烃b)的实例为:
1)芳族烃,例如
●经烷基单或多取代的芳族烃(例如经(C1-C10)烷基单、二或三取代的),例如苯类如甲苯、二甲苯、均三甲苯、乙苯,或
●具有稠合芳环系统的烃类,例如萘如1-甲基萘、2-甲基萘或二甲基萘,或其它稠合芳族烃,例如2,3-二氢化茚或1,2,3,4-四氢化萘,
2)脂环族烃类,例如
饱和或不饱和的、任选经烷基单或多取代的脂环族烃(例如经(C1-C10)烷基单、二或三取代的),例如环烷类、环烯类或环炔类,如环己烷或甲基环戊烷,
3)脂肪族烃类,例如
直链或支链的、饱和或不饱和的脂肪族烃,优选C5-C16-脂肪族烃,例如链烷类、链烯类或链炔类,如戊烷、己烷、辛烷、2-甲基丁烷或2,2,4-三甲基戊烷。
一种或多种芳族烃和/或一种或多种脂环族烃和/或一种或多种脂肪族烃的混合物也可以包含于组分b)。多种脂肪族烃混合物的实例,例如来自EXXSOLD系列、ISOPAR系列或BAYOL系列如Bayol82(EXXONMOBIL CHEMICALS),或来自ISANEIP系列或HYDROSEALG系列(TOTALFINAELF)的商购可得的溶剂,或芳族烃和脂肪族烃的混合物,例如来自SOLVESSO系列如Solvesso100、Solvesso150或Solvesso200(EXXONMOBIL CHEMICALS)、SOLVAREX/SOLVARO系列(TOTALFINAELF)或Caromax系列如Caromax28(Petrochem Carless)的商购可得的溶剂。
脂肪族烃类,尤其优选饱和的脂肪族烃,例如C5-C16-链烷烃,例如来自Bayol系列。
羧酸衍生物的实例为,例如羧酸酯类或羧酸酰胺类。
适宜的羧酸衍生物为,例如单羧酸、二羧酸或多羧酸(如三官能团或四官能团羧酸或具有更高官能度的羧酸,优选其具有2-26个碳原子)的酯类和酰胺类。
优选的酯为用C1-C20-醇(例如甲醇、乙醇、丙醇或丁醇)生成的酯;特别是在脂肪酸酯中丙三醇酯和乙二醇酯也是优选的。适宜的羧酸酯也可以为内在的酯如内酯。
单羧酸酯的实例为脂肪族和芳族单羧酸酯,例如脂肪族C1-C9-单羧酸酯如甲酸酯、乙酸酯和丙酸酯,或脂肪族的脂肪酸酯如C10-C22-脂肪酸酯,例如存在于天然油或植物油中的天然来源的化合物,或合成来源的化合物,或芳族C7-C22-单羧酸酯如苯甲酸酯或苯乙酸酯。
脂肪酸酯的实例为,例如天然来源的脂肪酸酯,例如天然油如动物油或植物油,或合成来源的脂肪酸酯,例如EdenorMESU或AGNIQUEME系列(COGNIS),SALIMME系列(SALIM)、STEPANC系列(STEPAN)或WITCONOL23系列(WITCO)。脂肪酸酯优选C10-C22-脂肪酸酯,更优选C12-C20-脂肪酸酯。C10-C22-脂肪酸酯为,例如不饱和或饱和的C10-C22-脂肪酸酯,尤其是具有偶数碳的脂肪酸酯,例如芥子酸、月桂酸、棕榈酸的酯,并且尤其优选C18-脂肪酸的酯,例如硬脂酸、油酸、亚油酸或亚麻酸的酯。
脂肪酸酯如C10-C22脂肪酸酯的实例为脂肪酸如C10-C22脂肪酸或其酯交换产物的丙三醇和乙二醇酯,例如脂肪酸的烷基酯如C10-C22脂肪酸的C1-C20烷基酯可通过将上述丙三醇或乙二醇脂肪酸酯如C10-C22脂肪酸酯与C1-C20醇(例如甲醇、乙醇、丙醇或丁醇)酯交换获得。酯交换反应可采用如Rmpp Chemie Lexikon,第9版,第2卷,1343页,Thieme Verlag Stuttgart中所述的已知方法进行。
优选的脂肪酸酯为,例如来自产油植物品种的油,例如大豆油、菜籽油、玉米油、向日葵油、棉籽油、亚麻子油、椰子油、棕榈油、红花油、核桃油、花生油、橄榄油或蓖麻油,尤其是菜籽油,植物油还应理解为指其酯交换产品,例如烷基酯如菜籽油甲酯或菜籽油乙酯。
二羧酸酯和多羧酸酯的实例为乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、癸二酸、壬二酸、辛二酸、马来酸、邻苯二甲酸、对苯二羧、苯六甲酸、三苯六甲酸和多马来酸的全酯,尤其是C1-C10-烷基酯如甲酯、乙酯、丙酯如正丙酯或异丙酯,丁酯如正丁酯、异丁酯、仲丁酯或叔丁酯。
其它适宜的羧酸酰胺为C1-C26-羧酸-N,N-二(C1-C20-烷基)-酰胺,例如C1-C26-羧酸-N,N-二甲基酰胺如N,N-二甲基甲酰胺或N,N-二甲基乙酰胺,或为内在的酰胺如内酰胺,例如吡咯烷酮,例如N-取代的C1-C12-烷基吡咯烷酮如N-甲基吡咯烷酮、N-丁基吡咯烷酮、N-辛基吡咯烷酮、N-十二烷基吡咯烷酮和N-环己基吡咯烷酮。
适宜的磷酸酯为,例如磷酸与醇的三酯,所述醇优选选自下组:
1)具有1-22个碳原子的单羟基烷醇,例如正-、异-或新-戊醇、正-己醇、正-辛醇、2-乙基己醇,
2)二醇或多元醇,例如乙二醇、丙二醇或丙三醇,
3)芳基-、烷基芳基-、聚(烷基)芳基-和聚(芳烷基)芳基醇,例如苯酚和/或甲苯酚、辛基苯酚、壬基苯酚、三异丁基苯酚、三苯乙烯基苯酚,
4)由如上所述1)、2)或3)的醇与环氧烷(优选(C1-C4)环氧烷)反应获得的烷氧基化醇。
优选的磷酸酯为邻-磷酸三酯,优选烷氧基化的邻-磷酸三酯,例如三(丁氧基乙基)磷酸酯。
适宜的酮为,例如芳族、脂环族或脂肪族酮,例如苯乙酮、二苯甲酮、异佛尔酮、环己酮和甲基乙基酮、乙基丁基酮、二乙基酮、二丁基酮。
适宜的醚为,例如芳族、脂环族或脂肪族醚,例如苯甲醚、四氢呋喃、环氧乙烷、二丁醚、二戊醚、丁基己基醚、甲基叔丁基醚。
优选的非醇类溶剂b)为芳族烃如C1-C6-烷基苯,例如甲苯或二甲苯,C1-C6-烷基萘,以及芳族烃的混合物例如来自Exxon的Solvesso系列,酮例如苯乙酮、异佛尔酮、环己酮和甲基乙基酮,N-取代的C1-C12-烷基吡咯烷酮如N-甲基吡咯烷酮、N-丁基吡咯烷酮、N-辛基吡咯烷酮、N-十二烷基吡咯烷酮和N-环己基吡咯烷酮,脂环族烃如十氢化萘和环己烷,酰胺类如二甲基甲酰胺、二甲亚砜,内酯如γ-丁内酯,二-或多羧酸酯如邻苯二甲酸的C1-C12-烷基酯,己二酸酯例如己二酸二异丙酯、己二酸二甲酯和己二酸二异丁酯,以及脂肪酸酯。
适宜的阴离子表面活性剂c)为,例如可以任选地包含环氧烷单元的烃类的硫酸盐、磺酸盐、磷酸盐和膦酸盐。该硫酸盐、磺酸盐、磷酸盐和膦酸盐可以以酸或盐形式存在。优选的阴离子表面活性剂c)为如下的式(I)化合物:
R-Q (I)
其中
Q为-O-SO3M、-SO3M、-O-PO3H M或PO3H M,
其中M为H或阳离子,尤其是金属离子如碱金属离子或碱土金属离子,或铵离子,
R为未经取代的或经取代的C1-C30-烃基,所述烃基可以任选地经由环氧烷单元连接,或R为环氧烷单元。
术语“环氧烷单元”应理解为尤其指C2-C10-环氧烷单元,如环氧乙烷、环氧丙烷或环氧丁烷,表面活性剂中的这些单元可以彼此相同或不同并且可以以无规混合或嵌段方式(blockweise)排列。
R优选为C1-C20-烷基(例如甲基、乙基、丙基、丁基),或C6-C24-芳基(例如苯基、联苯基、萘基),其可任选地带有一个或多个基团,例如选自带有一个或多个基团例如C6-C20-芳基(例如苯基、联苯基、萘基)的C1-C20-烷基(例如直链或支链C1-C20-烷基如仲丁基或十二烷基)和可任选地带有一个或多个基团如C1-C10-烷基(例如甲基、乙基、丙基、丁基)的C6-C20-芳基(例如苯基、联苯基或萘基),或
R为基团R2O-(AO)w,其中w为1至100的整数,并且AO为环氧烷单元,例如(EO)x(PO)Y(BO)Z,其中EO为环氧乙烷单元,PO为环氧丙烷单元,BO为环氧丁烷单元,x为0-100的整数,y为0-100的整数,z为0至100的整数,并且x+y+z之和至少为1,并且环氧烷单元如(EO)X(PO)Y(BO)Z可以以无规或嵌段方式构成,和
R2为H、C1-C20-烷基(例如甲基、乙基、丙基、丁基),或C6-C24-芳基(例如苯基、联苯基、萘基),其可任选带连有一个或多个基团如选自带有一个或多个基团例如C6-C20-芳基(例如苯基、联苯基、萘基)的C1-C20-烷基(例如直链或支链C1-C20-烷基如仲丁基或十二烷基)和可任选地带有一个或多个基团如C1-C10-烷基(例如甲基、乙基、丙基、丁基)的C6-C20-芳基(例如苯基、联苯基或萘基),或R2为-O-SO3M、-SO3M、-O-PO3H M、H或PO3H M,优选为PO3H M,其中M为H或阳离子,尤其是金属离子例如碱金属离子或碱土金属离子,或铵离子。
尤其优选的阴离子表面活性剂c)为烷基芳基磺酸盐例如十二烷基苯磺酸盐,如十二烷基苯磺酸的碱土金属盐如十二烷基苯磺酸钙(例如由Clariant制造的PhenylsulfonatCa100),烷基芳基聚乙二醇醚硫酸盐和磺酸盐,尤其是芳基烷基芳基聚乙二醇醚硫酸盐如三苯乙烯基苯基聚乙二醇醚硫酸盐,优选碱金属盐或铵盐或三乙醇胺盐(例如由Rhodia制造的Soprophore系列),烷基醚硫酸酯及其盐类(例如由Clariant制造的GenapolLRO),烷基硫酸盐和烷基磺酸盐(例如由Clariant制造Hostapur系列),烷基聚乙二醇醚磷酸盐,优选碱金属盐(例如由Rhodia制造的Rhodafac系列),烷基芳基聚乙二醇醚磷酸盐,优选以碱金属盐的形式。通常,上述盐优选为金属盐例如碱金属盐或碱土金属盐或铵盐或三烷基胺盐。
适宜的非离子表面活性剂d)为,例如烷氧基化物,例如乙氧基化物、丙氧基化物或丁氧基化物及其它们的组合。术语“烷氧基化物”应理解为指包含环氧烷单元(优选C2-C10-环氧烷单元,如环氧乙烷、环氧丙烷或环氧丁烷)的化合物,表面活性剂中的这些单元可以彼此相同或不同并且可以以无规或嵌段方式排列。烷氧基化物d)的实例为下式(II)化合物:
R1-(AO)w-R2 (II)
其中
R1为选自H、HO、可以是直链或支链的C1-C30-烷基的基团(例如甲基、乙基、丙基、丁基、戊基、己基)、可以是直链或支链的C1-C30-烷氧基,优选C1-C10-烷氧基(例如甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基)、任选连有一个或多个基团例如C1-C30-芳基烷基(例如苯乙烯基苯基)或可以为直链或支链的C1-C30-烷基(例如丁基或十二烷基)的C6-C24-芳基(例如苯基),或任选地连有一个或多个基团例如C1-C30-芳基烷基(例如苯乙烯基苯基)或可以为直链或支链的C1-C30-烷基(例如丁基或十二烷基)的C6-C24-芳氧基(例如苯氧基),或
R1为脱水山梨糖醇酯残基、丙三醇酯残基或C1-C30-烷基-NR4,优选C10-C20-烷基-NR4,其中C1-C20-烷基可以为直链或支链(例如十二烷基、十六烷基、十八烷基)并且其中R4为H或C1-C10-烷基(例如甲基、乙基、丙基、丁基),
R2为H或可以为直链或支链的C1-C6-烷基(例如甲基、乙基、丙基、丁基、戊基或己基),和
w为1至100的整数、AO为环氧烷单元,例如(EO)X(PO)Y(BO)Z,其中EO为环氧乙烷单元,PO为环氧丙烷单元,BO为环氧丁烷单元,x为0-100的整数,y为0-100的整数,z为0至100的整数,并且x+y+z之和至少为1,并且环氧烷单元如(EO)X(PO)Y(BO)Z是无规或嵌段方式构造的。
尤其优选的非离子表面活性剂d)为烷基芳基聚烷氧基化物,例如乙氧基化物、丙氧基化物和/或丁氧基化物,芳基烷基芳基聚烷氧基化物例如三苯乙烯基苯基聚烷氧基化物(例如由Rhodia制造的Soprophor系列)和烷基苯基聚烷氧基化物例如三丁基苯基聚烷氧基化物(例如由Clariant制造的Sopagenat系列),环氧烷嵌段共聚物例如环氧乙烷(EO)-环氧丙烷(PO)嵌段共聚物或环氧乙烷(EO)-环氧丁烷(BO)嵌段共聚物(例如由BASF制造的Pluronic系列),聚环氧烷例如聚环氧乙烷、聚环氧丙烷或聚环氧丁烷,其可以在两个末端氧原子之一上用C1-C22-烃基取代,优选为C10-C22-烃基如直链或支链C10-C22-烷基(例如癸基、十二烷基、十四烷基、十六烷基),例如可以被异十三烷基取代的聚乙二醇醚(例如由Clariant制造的Genapol系列),烷氧基化例如乙氧基化的油例如植物油,例如烷氧基化如乙氧基化的蓖麻油(由Clariant制造的Emulsogen系列),烷氧基化例如乙氧基化的(C10-C22)-脂肪胺(例如由Clariant制造的Genamin系列)。
当在具体情形下,本说明书所述的含碳基团,例如烷基、烷氧基、卤烷基、卤烷氧基、烷基氨基和烷硫基,以及相应的不饱和和/或经取代的基团的碳架可以为直链或支链。除非另有说明,这些基团通常具有1-30个碳原子,在此所述较低级的碳架例如具有1-6个碳原子,或在不饱和基团的情况下具有2-6个碳原子是优选的。烷基基团,以及在其复合意义如烷氧基、卤烷基等中为例如甲基、乙基、正-或异-丙基,正-、异-、叔-或仲-丁基、戊基、己基如正-己基、异-己基,以及1,3-二甲基丁基、庚基如正-庚基、1-甲基己基和1,4-二甲基戊基;烯基和炔基指相应烷基的可能不饱和基团;烯基如烯丙基、1-甲基丙-2-烯-1-基、2-甲基丙-2-烯-1-基、丁-2-烯-1-基、丁-3-烯-1-基、1-甲基丁-3-烯-1-基和1-甲基丁-2-烯-1-基;炔基为例如炔丙基、丁-2-炔-1-基、丁-3-炔-1-基、1-甲基丁-3-炔-1-基。
以(C3-C4)烯基、(C3-C5)烯基、(C3-C6)烯基、(C3-C8)烯基或(C3-C12)烯基形式的烯基优选为分别具有3至4、3至5、3至6、3至8和3至12个碳原子的烯基,其中双键没有在与式(I)化合物的剩余部分(“基”-位)相连的碳原子上。这也近似地适用于(C3-C4)炔基等、(C3-C4)烯氧基等和(C3-C4)炔氧基等。
烃基指直链、支链或环状的,并且是饱和或不饱和的脂肪族或芳族烃基团,例如烷基、烯基、炔基、环烷基、环烯基或芳基。
烃基优选具有1至40个碳原子,优选1至30个碳原子;烃基尤其优选具有多至12个碳原子的烷基、烯基或炔基或具有3、4、5、6或7个环原子的环烷基或苯基。
芳基为单、双或多环芳族系,例如苯基、萘基、四氢萘基、茚基、茚满基、环戊二烯基、芴基等,优选苯基。
杂环基或环(杂环基)可是饱和的、不饱和的或杂芳族的,并且是未经取代或经取代的;优选的是,环中包含一个或多个杂原子,杂原子优选选自N、O和S;优选为具有3至7个环原子的脂肪族杂环基或具有5或6个环原子的杂芳族基团,并且优选含有1、2或3个杂原子。杂环基可以为例如杂芳基或环(杂芳基)例如单、双或多环芳族系,其中至少一个环含有一个或多个杂原子,例如吡啶基、嘧啶基、哒嗪基、吡嗪基、三嗪基、噻吩基、噻唑基、噁唑基、呋喃基、吡咯基、吡唑基和咪唑基,或部分或完全氢化的基团如环氧乙烷基、氧杂环丁基、吡咯烷基、哌啶基、哌嗪基、二氧戊环基、吗啉基、四氢呋喃基。经取代的杂环基的适宜取代基为下文所述的取代基,以及还有氧代。氧代基团可以存在于可能有多个氧化数的杂环原子上,例如在N和S情形下。
卤素为例如氟、氯、溴或碘。卤烷基、-烯基和-炔基为烷基、烯基和炔基,它们部分或完全由卤素取代,优选由氟、氯和/或溴取代,尤其是由氟或氯取代,例如CF3、CHF2、CH2F、CF3CF2、CH2FCHCl、CCl3、CHCl2、CH2CH2Cl;卤烷氧基为例如OCF3、OCHF2、OCH2F、CF3CF2O、OCH2CF3和OCH2CH2Cl;这也同样的适用于卤烯基和其它经卤素取代的基团。
烃基,例如烷基、烯基、炔基、芳基、苯基和苄基或杂环基或杂芳基可以被取代,取代基指例如一个或多个,优选1、2或3个选自下组的基团:卤素、烷氧基、卤烷氧基、烷硫基、羟基、氨基、硝基、羧基、氰基、叠氮基、烷氧羰基、烷基羰基、甲酰基、氨甲酰基、单-和双烷基氨基羰基、经取代的氨基如酰氨基、单-和双烷基氨基,以及烷基亚磺酰基、卤烷基亚磺酰基、烷基磺酰基、卤烷基磺酰基,以及在环基团中也包括烷基和卤烷基,以及与上述饱和含烃基团相应的不饱和脂肪族基团,如烯基、炔基、烯氧基、炔氧基等。
具碳原子的基团中,具有1至4个碳原子、尤其是1或2个碳原子的基团是优选的。通常优选的是选自下组的取代基:卤素如氟和氯、(C1-C4)烷基(优选甲基或乙基)、(C1-C4)卤烷基(优选三氟甲基)、(C1-C4)烷氧基(优选甲氧基或乙氧基)、(C1-C4)卤氧基、硝基和氰基。本发明特别优选的是甲基、甲氧基和氯取代基。
任选的经取代的苯基优选未经取代或经选自下组的相同或不同基团单-或多取代的,优选多至三取代的苯基:卤素、(C1-C4)烷基、(C1-C4)烷氧基、(C1-C4)卤烷基、(C1-C4)卤烷氧基和硝基,例如邻、间和对甲苯基、二甲基苯基、2-、3-和4-氯苯基、2-、3-和4-三氟和三氯苯基、2,4-、3,5-、2,5-和2,3-二氯苯基、邻、间和对甲氧苯基。
酰基指形式上通过从有机酸除去OH基团形成的有机酸基团,例如羧酸基团和源自羧酸的基团,例如硫代羧酸,任选N-取代的亚氨基羧酸或碳单酯基团,任选N-取代的氨基甲酸、磺酸、亚磺酸、膦酸和亚膦酸。
酰基基团优选甲酰基或选自下组的脂肪族酰基:CO-Rx、CS-Rx、CO-ORx、CS-ORx、CS-SRx、SORY或SO2RY,其中Rx和RY分别为未经取代或经取代的C1-C30烃基,或氨基羰基或氨基磺酰基,最后所述的两个基团是未经取代的、经N-单取代的或N,N-双取代的。
酰基为例如甲酰基、卤烷基羰基、烷基羰基如(C1-C4)烷基羰基、苯基羰基,苯环是如上述苯基一样可以被取代的,或为烷氧基羰基、苯氧基羰基、苄氧基羰基、烷基磺酰基、烷基亚磺酰基、N-烷基-1-亚氨基烷基或其它有机酸基团。
本说明书中所述的式(I)和其它化合物还包括其所有的立体异构体及其混合物。这类化合物包含一个或多个不对称碳原子或其它的双键,这在通式中没有具体说明。由其特定的空间结构决定的可能的立体异构体,如对映异构体、非对映异构体,Z-和E-异构体均包含在各自的表达式中,并且可采用常规方法从立体异构体的混合物中获得的,或另外通过将立体选择反应与使用立体化学纯初始物质相结合获得的。
本发明的微乳剂可以采用常规方法加以制备,例如通过溶解或乳化各组分进行混和,优选于室温下进行。若还存在助剂和添加剂,也同样优选于室温下加入。通常,各组分可以以任何顺序加入。
该制备方法基本上是已知的,并例如在Winnacker-Küchler,“Chemische Technologie(化学技术)”,第7册,C.Hauser VerlagMünchen,第四版,1986;Wade van Valkenburg,“PesticideFormulations(农药制剂)”,Marcel Dekker N.Y.,1973;K.Martens,“Spray Drying Handbook(喷雾干燥手册)”,第三版,1979,G.GoodwinLtd.London;H.Mollet,A.Grubenmann,“Formulierungstechnik”[Formulation Technology](制剂工艺),Wiley-VCH,Weinheim 2000中有描述。
助剂例如惰性材料和其它的添加剂同样是已知的并描述于例如Watkins,“Handbook of Insecticide Dust Diluents and Carrier(杀虫粉尘稀释液和载体手册)”,第二版,Darland Books,CaldwellN.J.;H.v.Olphen,“Introduction to Clay Colloid Chemistry(粘土胶体化学入门)”,第二版,J.Wiley & Sons,N.Y.;C.Marsden,“Solvents Guide(溶剂指南)”,第二版,Interscience,N.Y.1963;McCutcheon′s,“Detergents and Emulsifiers Annual”,MC Publ.Corp.,Ridgewood N.J.;Sisley and Wood,“Encyclopedia of SurfaceActive Agents(表面活性剂百科全书)”,Chem.Publ.Co.Inc.,N.Y.1964;Schnfeldt,“Grenzflchenaktive thylenoxidaddukte(表面活性的环氧乙烷加成物)”,Wiss Verlagsgesell.,Stuttgart1976;Winnacker-Küchler,“Chemische Technologie”,第7册,C.Hauser Verlag München,第四版,1986中。
以这些制剂为基础,可以制备具有除a)之外的其它农业化学活性物质如除草剂、杀真菌剂、杀虫剂以及安全剂、肥料和/或生长调节剂的组合物,例如以预混物或者桶混合形式。
本发明的微乳剂可以用水稀释以获得微乳液,这同样地是本发明的主题。微乳剂与水的重量比可以为例如1∶0.1至1∶100,优选为1∶1至1∶100,以此获得储藏稳定的浓缩的微乳液。对于施用,其可以进一步用水进行稀释,获得通常以乳液如微乳液、水溶液、悬浮液、悬乳液形式存在的喷雾混合物。
本发明的微乳剂组分a)、b)、c)和d)和微乳液可以在成品制剂中被包含,所述成品制剂随后可以以常规方式施用,例如以喷雾混合物的方式。
除组分a)、b)、c)和d)外,本发明的微乳剂和微乳液,以及包括由微乳剂和微乳液获得的喷雾组合物(下文均称作本发明的农业化学组合物),还可包含作为其它组分的常规助剂和添加剂,例如制剂助剂如抗漂浮剂、湿润剂、肥料如硫酸铵、尿素或如基于磷、钾和氮的多组分肥料化合物,例如P、K、N-肥料,或除组分c)和d)外的商购可得的表面活性剂例如内铵盐型或聚合物型表面活性剂,稳定剂如pH稳定剂、生物杀灭剂、UV稳定剂、消泡剂、合成或天然聚合物、溶剂例如极性溶剂如水,或非极性溶剂如可以为直链或支链的饱和或非饱和脂肪族溶剂,或芳族溶剂例如Solvesso100、Solvesso150或Solvesso200或二甲苯。该农业化学组合物及其制备和用途同样是新的并且也是本发明的主题。
优选的常规助剂和添加剂实例为
●湿润剂如GenapolLRO(0-20重量%),分散剂如Tamol(0-15重量%)或其它表面活性剂(非离子、阳离子、阴离子、聚合物表面活性剂)(0-30重量%);
●无机盐如NaCl、Na2SO4、MgCl2(0-50重量%)、(寡-,聚-)磷酸盐;碳酸盐如碳酸钾;
●肥料如硫酸铵、硝酸铵、尿素、含磷和含钾组分,视需要的其它微量元素(0-60重量%);
●消泡剂,例如FluowetPP(0-2重量%);
●粘合剂如适宜的天然或合成物质如聚氨基酸、聚乙烯醇、聚乙烯吡咯烷酮、聚丙烯酸衍生物(0-15重量%);或
●溶剂如水或有机溶剂(0-15重量%)。
本发明的农业化学组合物可通过例如采用喷雾法施用至有害生物体或其出没的场所。通常,本发明的农业化学组合物以喷雾混合物的形式施用,其包含有效量的组分a)、b)、c)和d)和视需要加入另外的常规助剂和添加剂,例如用于配制和使用的。通常,该喷雾混合物基于水配制,其可以添加常规助剂和添加剂,例如油如植物油,或高沸点烃类如煤油或石蜡。
施用中,以施用量为1至5000l/ha,优选50至1000l/ha施用组合物例如喷雾混合物,农业化学活性成分a)的浓度通常为10-6至10重量%,优选为10-5至4重量%。
就使用而言,将商购可得形式的浓缩制剂视需要以常规方式稀释,例如用水稀释。将更多量的组分b)、c)和d)和/或其它用于施用的常规助剂和添加剂加至喷雾混合物中是有利的,尤其是自乳化油(self-emulsifying oils)或石蜡油。也可以加入额外的组分a)或不同于a)的其它的农业化学活性成分。
所需的农业化学活性成分a)的施用量可随着外部条件如温度、湿度和所使用除草剂的类型而不同。该施用量可在大范围内变化,例如介于0.001和10kg/ha之间或更多的活性物质;优选介于0.005和5kg/ha之间。
本发明的农业化学组合物优选为除草组合物。该组合物对广谱性的经济重要的单子叶和双子叶有害植物具有显著的除草活性。该活性成分也有效地作用于从根茎、根状茎或其它多年生器官发芽的、并且难于控制的多年生杂草。本文中,该活性物质可以例如播种前、苗前或苗后施用。可提及的特定的实例中本发明的除草组合物可控制一些具有代表性的单子叶和双子叶杂草植物,而该列举不限于特定种类。
在单子叶杂草种类中,本发明除草组合物有效作用的例如一年生的主要有风剪股颖属、燕麦草属、看麦娘属、臂形草属、马唐属、黑麦草属、稗草属、黍属、
草属、早熟禾属、粟属和雀麦属,例如扁穗雀麦、黑麦状雀麦、直立雀麦、早雀麦和雀麦,和莎草属如一年生的小麦草属、狗牙根属、白茅属、高梁属和多年生的莎草属。
在双子叶杂草类实例中,作用谱扩大至如下的种类,例如一年生的苘麻属、苋属、藜属、茼蒿属、猪殃殃属如猪殃殃、番薯属、地肤属、野芝麻属、母菊属、牵牛花属、寥属、黄花稔属,白芥属、茄属、繁缕属、婆婆纳属和堇菜属、苍耳属,以及多年生的旋花属、蓟属、酸模属、蒿属的杂草。
本发明的活性物质也能显著地控制发生于特定的稻米生长条件下的有害植物如例如稗、慈姑、泽泻、荸荠、蔗草及莎草。
若将本发明的除草组合物苗前施用至土壤表面,则杂草苗的发芽完全被阻止了,或杂草生长至子叶期,但随后停止生长,并且3至4周后完全停止生长,最后死亡。
若将本发明的除草组合物苗后施用至植物的绿色部分,处理后的短时间内生长同样地急剧停止,并且杂草植物保持在施用时间的发育阶段,或一段时间后完全死亡,从而在早期以这种持续的方式消除了对作物有害的杂草竞争。
本发明的除草组合物具有显著的迅速起效和长效的除草作用。通常来说,本发明组合物中的活性化合物具有利的耐雨水性。尤其有利的是用于该除草组合物中的剂量和除草组合物的有效剂量可调至低水平,使得对土壤的作用最小。由此本发明的组合物不仅能够用于敏感作物中,而且实际上避免了对地下水的污染。本发明的活性物质的组合使得活性物质的所需施用量得以大大地减少。
上述特征和优点在保持农作物摆脱不期望的竞争植物的杂草控制实践中是有利的,从而在质量上和数量上确保和/或提高了产量水平。该新组合物显著地优于现有技术产品所具有的性能。
虽然本发明的除草组合物控制单子叶和双子叶杂草具显著的除草活性,然而对经济重要性作物,例如双子叶作物如大豆、棉花、油菜、甜菜、或禾本科作物例如小麦、大麦、黑麦、高梁、粟、水稻或玉米,仅有非实质性损害或根本没有损害。出于这些原因,本发明化合物高度适用于农作物或观赏植物种植中选择性控制不需要的植物生长。
此外,本发明除草组合物在作物中具有显著的生长调节性能。它们以调节性的方式参与植物的新陈代谢,并且从而可用于直接影响植物内容物,并且通过例如引发脱水和生长停滞以促进产量。此外,它们还适用于常规的控制和抑制不需要的植物生长,而非就此杀死植物。由于从而可减少或完全预防倒伏,因此植物生长的抑制在大多数单子叶和双子叶作物中扮演着相当重要的角色。
由于其除草和植物生长调节性质,本发明的除草组合物可用于控制已知的或仍在开发的基因工程植物中的有害植物。转基因植物通常具有特别优越的性质,例如对某些农药的抗性,尤其是某些除草剂、对植物病害或植物病害病原体,如某些昆虫或微生物如真菌、细菌或病毒的抗性。其它的特殊性质涉及例如收成产物的数量、质量、储藏性能、组分和特定成分。因此,转基因植物以经提高的淀粉含量或经改良的淀粉品质或那些具有不同的脂肪酸组分的收成产物而著称。
优选将本发明的除草组合物用于具经济重要性的转基因作物和观赏植物,例如禾本科作物如小麦、大麦、黑麦、燕麦、高梁和粟,水稻和玉米,或其它作物甜菜、棉花、大豆、油菜、马铃薯、西红柿、豌豆和其它植物。优选地,本发明组合物作为除草剂用于针对除草剂毒性作用耐受的或通过基因工程技术使之耐受的有用作物中。
当将本发明的除草组合物用于转基因作物时,除观察到在其它作物中对抗有害植物的效果外,还经常观察到施用在所述的转基因作物上的特定效果,例如可控制改变的或特殊扩大的杂草谱,可用于施用的改变的施用量,优选同对于转基因作物有抗性的除草剂的良好结合性,以及对转基因作物生长和产量水平的影响。
因此,本发明还进一步涉及了一种用于控制不需要植物的方法,优选用于作物中如谷类(例如小麦、大麦、黑麦、燕麦、水稻、玉米、高梁和粟)、甜菜、甘蔗、油菜、棉花和大豆,尤其优选用于单子叶植物中,例如谷类如小麦、大麦、黑麦、燕麦,以及它们的杂交种如黑小麦、水稻、玉米、高梁和粟,其中将一种或多种本发明的除草组合物例如苗前、苗后或苗前和苗后,优选苗前施用至有害植物、植物局部、植物种子或这些植物生长的区域如栽培区域。
这些作物也可以为基因改良的或通过突变选择获得的,优选为耐受乙酰乳酸合成酶(ALS)抑制剂的作物。
本发明还涉及将本发明的除草组合物用于控制有害植物、优选在作物中控制有害植物的用途。优选的用途涉及施用包含增效量的组分a)、b)、c)和d)的除草组合物。
本发明的除草组合物还可用于非选择性地控制不需要的植物,例如在作物种植中、路边、广场、工厂或铁轨边。
本发明的农业化学组合物,尤其是除草组合物可以视需要以混和制剂形式与其它农业化学活性成分和常规助剂和添加剂相混和,并且该混和制剂随后以常规方式用水稀释应用,或以所谓桶混物形式由分开配制或部分分开配制的组分用水制备。
由于本发明除草组合物相对低的施用量,它们通常具有良好的相容性。特别是,与单独使用除草活性物质相比,采用本发明的组合物可使绝对施用量得以降低。
因此本发明还涉及一种选择性控制作物中有害植物的方法,该方法包括例如苗前、苗后或苗前和苗后,优选苗前,将除草活性量的上述除草除草剂a)与组分b)、c)和d)相混和施用至植物、植物局部、植物种子或植物生长区域,例如耕作区域。
在优选的派生方法中,除草剂a)以施用量为0.1至2000g的活性物质/ha,优选0.5至1000g的活性物质/ha进行施用。此外尤其优选的是以共制剂或桶混物形式施用活性物质,用水将单个组分(例如以制剂形式)在桶中一并混和,并且将所得的喷雾混合物进行施用。
由于本发明组合物在高度控制有害植物的同时与作物的相容性非常好,因此可以认为本发明的组合物是选择性的。因此在优选的派生方法中,将本发明具有活性物质组合物的除草组合物用于选择性控制不需要的植物。
视需要,本发明除草组合物的相容性和/或选择性甚至还可以进一步提高,将其与安全剂或解毒剂以混合物形式一并施用或时间上交错地施用是有利的。
适用于本发明除草组合物的安全剂或解毒剂的化合物是已知的,例如描述于EP-A-333 131(ZA-89/1960)、EP-A-269 806(US-A-4,891,057)、EP-A-346 620(AU-A-89/34951),以及国际专利申请PCT/EP 90/01966(WO-91108202)和PCT/EP 90102020(WO-911078474),以及其中所引用的文献中,或可通过其所描述的方法制备的。其它适宜的安全剂得知于EP-A-94 349(US-A-4,902,304)、EP-A-191 736(US-A-4,881,966)和EP-A-0492 366,及其所引用的文献中。
因此在优选的实施方式中,本发明的除草组合物包含额外量的一种或多种用作安全剂或解毒剂的化合物。
适合作为安全剂或解毒剂用于本发明上述除草组合物中的特别优选的安全剂或解毒剂或化合物组尤其是:
a)二氯苯基吡唑啉-3-羧酸类化合物,优选化合物例如描述于国际专利申请WO 91/07874(PCT/EP 90102020)中的1-(2,4-二氯苯基)-5-(乙氧羰基)-5-甲基-2-吡唑啉-3-羧酸乙酯(化合物S1-1,吡咯二酸二乙酯),以及相关化合物;
b)二氯苯基吡唑羧酸衍生物,优选化合物例如EP-A-0 333 131和EP-A-0 269 806中所述的1-(2,4-二氯苯基)-5-甲基吡唑-3-羧酸乙酯(化合物S1-2)、1-(2,4-二氯苯基)-5-异丙基吡唑-3-羧酸乙酯(化合物S1-3)、1-(2,4-二氯苯基)-5-(1,1-二甲基乙基)吡唑-3-羧酸乙酯(化合物S1-4)、1-(2,4-二氯苯基)-5-苯基吡唑-3-羧酸乙酯(化合物S1-5),以及相关化合物;
c)噻唑羧酸类化合物,优选化合物例如1-(2,4-二氯苯基)-5-三氯甲基-(1H)-1,2,4-三唑-3-羧酸乙酯(化合物S1-6,解草唑)以及相关化合物(参见EP-A-0 174 562和EP-A-0 346 620);
d)二氯苄基-2异噁唑啉-3-羧酸类化合物,5-苄基-或5-苯基-2-异噁唑啉-3-羧酸类化合物,优选化合物如描述于国际专利申请WO91/08202(PCT/EP 90/01966)中的5-(2,4-二氯苄基)-2-异噁唑啉-3-羧酸乙酯(化合物S1-7)或5-苯基-2-异噁唑啉-3-羧酸乙酯(化合物S1-8)以及相关化合物;
e)8-喹啉氧基乙酸类化合物,优选化合物如描述于EP-A-0 086750、EP-A-0 094 349和EP-A-0 191 736或EP-A-0 492 366中的1-甲基己-1-基(5-氯-8-喹啉氧基)乙酸酯(S2-1,解草酯),
1,3-二甲基-丁-1-基(5-氯-8-喹啉氧基)乙酸酯(S2-2),
4-烯丙氧基丁基(5-氯-8-喹啉氧基)乙酸酯(S2-3),
1-烯丙氧基丙-2-基(5-氯-8-喹啉氧基)乙酸酯(S2-4),
(5-氯-8-喹啉氧基)乙酸乙酯(S2-5),
(5-氯-8-喹啉氧基)乙酸甲酯(S2-6),
(5-氯-8-喹啉氧基)乙酸烯丙酯(S2-7),
2-(2-亚丙基亚氨基氧基)-1-乙基(5-氯-8-喹啉氧基)乙酸酯(S2-8),
2-氧丙-1-基(5-氯-8-喹啉氧基)乙酸酯(S2-9)以及相关化合物;
f)(5-氯-8-喹啉氧基)丙二酸类化合物,优选化合物例如描述于德国专利申请EP-A-0 582 198中的(5-氯-8-喹啉氧基)丙二酸二乙酯、(5-氯-8-喹啉氧基)丙二酸二烯丙酯、(5-氯-8-喹啉氧基)丙二酸甲基乙基酯以及相关化合物;
g)苯氧乙酸、苯氧丙酸衍生物或芳族羧酸类活性化合物,例如2,4-二氯苯氧乙酸及其酯(2,4-D)、4-氯-2-甲基苯氧丙酸(2甲4氯丙酸)、MCPA或3,6-二氯-2-甲氧基-苯甲酸及其酯(麦草畏)。
h)5,5-二苯基-2-异噁唑啉-3-羧酸类化合物,优选5,5-二苯基-2-异噁唑啉-3-羧酸乙酯(S3-1,双苯唑酸乙酯)。
i)已知的安全剂化合物,例如用于水稻的,如解草啶(=4,6-二氯-2-苯基嘧啶,Pesticide Manual(农药手册),第11版,1997,511-512页),哌草丹(=哌啶-1-硫代甲酸S-1-甲基-1-苯基乙基酯,Pesticide Manual,第11版,1997,404-405页),杀草隆(=1-(1-甲基-1-苯基乙基)-3-对-甲苯基脲,Pesticide Manual,第11版,1997,330页),苄草隆(=3-(2-氯苯基甲基)-1-(1-甲基-1-苯基乙基)脲,JP-A-60/087254),苯草酮(=3,3’-二甲基-4-甲氧基苯甲酮,CSB(=1-溴-4-(氯甲基磺酰基)苯,CAS-Reg.Nr.54091-06-4)。
此外,上述化合物至少部分描述于EP-A-0 640 587中,该文献由此引入作为参考。
j)适合作为安全剂和解毒剂的其它重要的化合物组已知于WO95/07897和WO 99/16744中。
当将本发明的除草组合物用于有用作物时,上述a)至j)组的安全剂(解毒剂)会出现降低或防止植物毒性的作用,而对控制有害植物的除草活性无不利影响。这极大地扩大了本发明除草组合物的施用谱;尤其是,利用安全剂能施用先前仅用于有限范围或不足够有效的除草组合物,即无安全剂情况下低剂量施用该组合物,导致不能有效控制有害植物并且显示低的广谱活性。
本发明除草组合物的组分a)、b)、c)和d)与上述的安全剂可一起施用(例如以成品制剂或桶混方式)或以任意顺序先后施用。安全剂与除草剂的重量比可在很大范围内变化,并且优选范围为1∶100至100∶1,尤其优选1∶100至50∶1。除草剂和安全剂的最佳量通常取决于所使用的除草剂组合物和/或安全剂的类型,以及待处理的植物种类。
根据其性质,安全剂可用于预处理作物种子(种子处理),或通过植物种植前混入或苗前或苗后与除草剂混合物一起施用。苗前处理不仅包括在播种前处理耕作区域,而且包括处理已经播种作物但没有发芽的耕作区域。与除草剂混合物一起施用是优选的。桶混物或成品制剂可用于此。
根据指示和所用的除草剂,所需安全剂的施用量可在很大范围内变化;通常该范围为0.001至1kg,优选0.005至0.2kg的活性物质/公顷。
本发明的除草组合物可以以常规方法施用,例如在喷雾混合物中用水作为载体,水量约为5至4000升/ha。以已知的低量或超低量方法(ULV)施用该组合物也是可以的。
此外,为了补充性能,本发明的除草组合物还可以包含除草剂a)以外的一种、两种或多种农业化学活性物质(例如杀虫剂、杀真菌剂、安全剂),通常以较少的量。
这引起将多个农业化学活性成分彼此组合以及将其一并用于控制作物中的有害生物体如有害植物的大量可能性,而不偏离本发明的实质。
在一个实施方式中,例如不同的农业化学活性成分可以彼此组合,例如精噁唑禾草灵乙酯/碘苯腈辛酸酯、禾草灵/溴苯腈辛酸酯、CMPP/溴苯腈辛酸酯、MCPA/碘苯腈辛酸酯、溴苯腈辛酸酯/溴苯腈庚酸酯、溴苯腈辛酸酯/溴苯腈庚酸酯/MCPA、溴苯腈辛酸酯/溴苯腈庚酸酯/2,4-D、甜菜宁/甜菜安、甜菜宁/甜菜安/乙氧呋草黄、苯嗪草酮/乙氧呋草黄、甜菜宁/乙氧呋草黄/苯嗪草酮、精噁唑禾草灵乙酯/碘甲磺隆钠盐、溴氰菊酯/氯氰菊酯。
除草活性成分a)及其混合物,例如上述的活性成分混合物,可以与一种或多种安全剂相组合,优选与安全剂吡咯二酸二乙酯(S1-1)、解草酯(S2-1)、双苯噁唑酸-乙酯(S3-1)或解草唑-乙酯(S1-6)相组合,优选与(S1-1)、(S2-1)或(S3-1)相组合。
出人意外地,本发明的微乳剂用水稀释提供稳定的微乳液,无需使用醇类溶剂。
本发明的微乳剂和微乳液显示了良好的物理施用性状。在施用期间,农业化学活性成分保持均一地分散在喷雾桶中,使其能均一地施用至作物或栽培区域。即使在喷雾桶中形成的混合物(桶混物)如水溶液、悬浮液、乳液或悬乳液也是稳定的。
本发明的农业化学组合物显示了显著的生物活性以及优选的增效作用。该效果尤其让施用量得以降低、可控制更广谱的有害生物、克服控制缺口、更迅速和更安全的作用、延长作用时间、仅用一次或少数几次施用完全控制有害生物,并且拓宽了施用范围。
利用下面的实施例说明本发明但不限定任何特征。
实施例
制剂的制备
首先将农业化学活性物质加至搅拌的溶剂中,随后加入表面活性剂和常规助剂以及添加剂。从而随后按照比例为1∶10、1∶30和1∶100,向所制备的微乳剂中加入水。获得微乳液。将该微乳液于50摄氏度下储藏3个月,在整个储藏期间该微乳液保持稳定。
在表1和2中,所组合成分的量以重量%表示。
表1
实施例 | 1 | 3 | 4 | 5 | 6 |
精噁唑禾草灵乙酯 | 5 | 0 | 0 | 0 | 0 |
吡咯二酸二乙酯 | 0 | 9 | 0 | 0 | 0 |
碘甲磺隆钠盐 | 0 | 3 | 0 | 0 | 0 |
溴苯腈-辛酸酯 | 0 | 0 | 15 | 0 | 0 |
CMPP-异丁酯 | 0 | 0 | 0 | 10 | 0 |
叠磺隆-甲酯 | 0 | 0 | 0 | 0 | 1 |
Solvesso 200 | 33 | 25 | 26 | 32 | 35 |
磷酸三乙酯 | 12 | 0 | 0 | 0 | 0 |
N-甲基-吡咯烷酮 | 0 | 12 | 10 | 10 | 15 |
Arkopal N100 | 20 | 20 | 20 | 0 | 0 |
Sapogenat T-100 | 0 | 0 | 0 | 20 | 20 |
Emulsogen V1816 | 10 | 10 | 12 | 10 | 12 |
Triton GR 7ME | 0 | 15 | 0 | 0 | |
Phenylsulfonat Ca100 | 12 | 0 | 10 | 10 | 10 |
Genapol PF 40 | 6 | 4 | 5 | 6 | 5 |
Edenol D 81 | 2 | 2 | 2 | 2 | 2 |
合计: | 100 | 100 | 100 | 100 | 100 |
表2
实施例 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
甜菜安 | 2.50 | 0 | 0 | 0 | 2.41 | 2.41 | 0 | 0 |
乙氧呋草黄 | 0 | 14.75 | 0 | 0 | 0 | 14.75 | 14.75 | 4.75 |
苯嗪草酮 | 0 | 0 | 2.50 | 0 | 0 | 0 | 0 | 2.00 |
甜菜宁 | 0 | 0 | 0 | 7.30 | 7.30 | 0 | 7.30 | 7.30 |
Solvesso 200 | 34.70 | 22.45 | 34.70 | 39.18 | 32.77 | 25.32 | 20.43 | 28.43 |
磷酸三乙酯 | 10.00 | 10.00 | 10.00 | 10.00 | 5.00 | 5.00 | 5.00 | 5.00 |
N-甲基-吡咯烷酮 | 0 | 0 | 0 | 0 | 5.00 | 5.00 | 5.00 | 5.00 |
实施例 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
Emulsogen V1816 | 10.00 | 10.00 | 10.00 | 8.00 | 10.00 | 10.00 | 10.00 | 10.00 |
Phenylsulfonat Cal00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 |
Genapol X-060 | 0 | 23.80 | 23.80 | 0 | 0 | 0 | 0 | 0 |
Genapol X-080 | 0 | 0 | 0 | 18.52 | 18.52 | 18.52 | 18.52 | 18.52 |
Genapol PF 40 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 |
Edenol D 81 | 3.00 | 3.00 | 3.00 | 1.00 | 3.00 | 3.00 | 3.00 | 3.00 |
合计: | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
所使用的商购产品如下详细描述:
Solvesso 200(Exxon):芳烃混合物
Arkopal N 100(Clariant):具有10个环氧乙烷单元的壬基苯基乙氧基化物
Sapogenat T-100(Clariant):具有10个环氧乙烷单元的三异丁基苯酚乙氧基化物
Emulsogen V 1816(Clariant):PO-EO-嵌段共聚物
Triton GR 7 ME(Union Carbide):二(2-乙基己基)磺基琥珀酸酯
Phenylsulfonat Ca 100(Clariant):十二烷基苯磺酸钙
Genapol X-060(Clariant):具有6个环氧乙烷单元的异十三醇
Genapol X-080(Clariant):具有8个环氧乙烷单元的异十三醇
Genapol PF 40(Clariant):EO-PO-EO-嵌段共聚物
Edenol D 81(Cognis):环氧化的豆油
Claims (17)
1.一种微乳剂,其包含
a)一种或多种农业化学活性成分,
b)一种或多种非醇类有机溶剂,
c)一种或多种阴离子表面活性剂,和
d)一种或多种非离子表面活性剂。
2.根据权利要求1的微乳剂,其特征在于,包含作为组分a)的一种或多种除草活性成分。
3.根据权利要求1或2的微乳剂,其特征在于,包含作为组分b)的一种或多种选自烃类、羧酸衍生物类、磷酸酯类、醚类、酮类或亚砜类的溶剂。
4.根据权利要求1-3一项或多项所述的微乳剂,其特征在于,包含作为组分c)的一种或多种阴离子表面活性剂,选自可任选被烷氧基化的烃类的硫酸盐、磺酸盐、磷酸盐和膦酸盐,优选烷基芳基磺酸盐、烷基芳基聚乙二醇醚磷酸盐硫酸盐、烷基芳基聚乙二醇醚磷酸盐磺酸盐、烷基醚硫酸盐、烷基硫酸盐、烷基磺酸盐、烷基聚乙二醇醚磷酸盐和烷基芳基聚乙二醇醚磷酸盐。
5.根据权利要求1-4一项或多项所述的微乳剂,其特征在于,包含作为组分d)的一种或多种选自烷氧基化物的非离子表面活性剂,优选为烷基芳基聚烷氧基化物、环氧烷嵌段共聚物、可以经C10-C22-烃基取代的聚环氧烷、烷氧基化的油、烷氧基化的C10-C22-脂肪胺。
6.根据权利要求1-5一项或多项所述的微乳剂,其特征在于,还另外包含常规的助剂和添加剂。
7.一种用于制备权利要求1-6一项或多项所述的微乳剂的方法,其特征在于,将各组分进行混合。
8.将权利要求1-6一项或多项所述的微乳剂用于制备微乳液的用途。
9.一种农业化学组合物,其包含
a)一种或多种农业化学活性成分,
b)一种或多种非醇类有机溶剂,
c)一种或多种阴离子表面活性剂,
d)一种或多种非离子表面活性剂,和
e)水。
10.根据权利要求9的农业化学组合物,其特征在于,还另外包含常规的助剂和添加剂。
11.根据权利要求9或10所述的农业化学组合物,其特征在于,可以由此获得微乳液或喷雾混合物的形式。
12.一种农业化学组合物,其特征在于,该组合物可通过用水稀释权利要求1-6一项或多项所述的微乳剂获得的。
13.一种制备权利要求9-12一项或多项所述的农业化学组合物的方法,其特征在于,将各组分进行混合。
14.一种控制有害生物体的方法,其特征在于,将有效量的权利要求1-6或9-12一项或多项所述的农业化学组合物施用至有害生物体或其出没的场所。
15.一种控制不需要的植物的方法,其特征在于,将有效量的权利要求1-6或9-12一项或多项所述的农业化学组合物施用至有害植物、植物局部、植物种子、植物生长区域。
16.将权利要求1-6或9-12一项或多项所述的农业化学组合物用于控制有害生物体的用途。
17.根据权利要求16的用途,其特征在于,有害生物体为有害植物。
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DE10258867A DE10258867A1 (de) | 2002-12-17 | 2002-12-17 | Mikroemulsionskonzentrate |
DE10258867.8 | 2002-12-17 |
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US (1) | US20040132621A1 (zh) |
EP (1) | EP1575357A2 (zh) |
JP (1) | JP2006509807A (zh) |
KR (1) | KR20050088183A (zh) |
CN (1) | CN1725951A (zh) |
AU (1) | AU2003293763A1 (zh) |
BR (1) | BR0317398A (zh) |
CA (1) | CA2510028A1 (zh) |
DE (1) | DE10258867A1 (zh) |
EA (1) | EA200500965A1 (zh) |
HR (1) | HRP20050564A2 (zh) |
IL (1) | IL169126A0 (zh) |
MX (1) | MXPA05006483A (zh) |
PL (1) | PL377773A1 (zh) |
RS (1) | RS20050446A (zh) |
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CN1903029A (zh) * | 2005-07-27 | 2007-01-31 | 拜尔农作物科学有限公司 | 微乳剂 |
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-
2002
- 2002-12-17 DE DE10258867A patent/DE10258867A1/de not_active Ceased
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2003
- 2003-12-04 RS YUP-2005/0446A patent/RS20050446A/sr unknown
- 2003-12-04 EA EA200500965A patent/EA200500965A1/ru unknown
- 2003-12-04 CN CNA2003801063722A patent/CN1725951A/zh active Pending
- 2003-12-04 KR KR1020057011098A patent/KR20050088183A/ko not_active Application Discontinuation
- 2003-12-04 BR BR0317398-4A patent/BR0317398A/pt not_active IP Right Cessation
- 2003-12-04 AU AU2003293763A patent/AU2003293763A1/en not_active Abandoned
- 2003-12-04 WO PCT/EP2003/013693 patent/WO2004054360A2/de active Application Filing
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US20040132621A1 (en) | 2004-07-08 |
ZA200504443B (en) | 2005-11-22 |
DE10258867A1 (de) | 2004-07-08 |
CA2510028A1 (en) | 2004-07-01 |
JP2006509807A (ja) | 2006-03-23 |
AU2003293763A1 (en) | 2004-07-09 |
KR20050088183A (ko) | 2005-09-02 |
IL169126A0 (en) | 2009-02-11 |
BR0317398A (pt) | 2005-11-16 |
WO2004054360A3 (de) | 2004-10-07 |
RS20050446A (en) | 2008-04-04 |
WO2004054360A2 (de) | 2004-07-01 |
PL377773A1 (pl) | 2006-02-20 |
MXPA05006483A (es) | 2005-08-26 |
HRP20050564A2 (en) | 2006-07-31 |
EA200500965A1 (ru) | 2005-12-29 |
EP1575357A2 (de) | 2005-09-21 |
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