CN101911949A - Fungicide composition containing prochloraz and L-α-terpineol and production method thereof - Google Patents
Fungicide composition containing prochloraz and L-α-terpineol and production method thereof Download PDFInfo
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- CN101911949A CN101911949A CN201010253306XA CN201010253306A CN101911949A CN 101911949 A CN101911949 A CN 101911949A CN 201010253306X A CN201010253306X A CN 201010253306XA CN 201010253306 A CN201010253306 A CN 201010253306A CN 101911949 A CN101911949 A CN 101911949A
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- Prior art keywords
- terpineol
- prochloraz
- handed alpha
- solvent
- alpha
- Prior art date
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Links
- 239000005820 Prochloraz Substances 0.000 title claims abstract description 77
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 230000000855 fungicidal effect Effects 0.000 title abstract description 3
- 239000000417 fungicide Substances 0.000 title abstract description 3
- WUOACPNHFRMFPN-VIFPVBQESA-N (R)-(+)-alpha-terpineol Chemical compound CC1=CC[C@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-VIFPVBQESA-N 0.000 title abstract 3
- 239000003921 oil Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 26
- -1 monoterpene alcohols Chemical class 0.000 claims abstract description 22
- 239000003899 bactericide agent Substances 0.000 claims abstract description 18
- 235000004936 Bromus mango Nutrition 0.000 claims abstract description 15
- 235000014826 Mangifera indica Nutrition 0.000 claims abstract description 15
- 235000009184 Spondias indica Nutrition 0.000 claims abstract description 15
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 13
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 11
- 239000004480 active ingredient Substances 0.000 claims abstract description 11
- 235000009566 rice Nutrition 0.000 claims abstract description 11
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims abstract description 10
- 229940116411 terpineol Drugs 0.000 claims abstract description 10
- 240000007228 Mangifera indica Species 0.000 claims abstract 2
- 240000008790 Musa x paradisiaca Species 0.000 claims abstract 2
- 240000007594 Oryza sativa Species 0.000 claims abstract 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims description 70
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims description 70
- 229940088601 alpha-terpineol Drugs 0.000 claims description 70
- 235000019198 oils Nutrition 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 230000003641 microbiacidal effect Effects 0.000 claims description 21
- 229940124561 microbicide Drugs 0.000 claims description 21
- 239000002855 microbicide agent Substances 0.000 claims description 21
- 239000008213 purified water Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000006184 cosolvent Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000013530 defoamer Substances 0.000 claims description 9
- 239000002562 thickening agent Substances 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 6
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 6
- DMAXMXPDVWTIRV-UHFFFAOYSA-N 2-(2-phenylethyl)phenol Chemical compound OC1=CC=CC=C1CCC1=CC=CC=C1 DMAXMXPDVWTIRV-UHFFFAOYSA-N 0.000 claims description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 4
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003905 agrochemical Substances 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- 229930182478 glucoside Natural products 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 230000002528 anti-freeze Effects 0.000 claims description 3
- 230000000443 biocontrol Effects 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 2
- 229920000896 Ethulose Polymers 0.000 claims description 2
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 11
- 201000010099 disease Diseases 0.000 abstract description 10
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 239000001293 FEMA 3089 Substances 0.000 abstract description 2
- 230000001934 delay Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229930003658 monoterpene Natural products 0.000 abstract description 2
- 235000002577 monoterpenes Nutrition 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 206010059866 Drug resistance Diseases 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000002552 dosage form Substances 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- 241001093152 Mangifera Species 0.000 description 13
- 239000003814 drug Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 230000003449 preventive effect Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 241000209094 Oryza Species 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 241000234295 Musa Species 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- 235000013399 edible fruits Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000011835 investigation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000005822 Propiconazole Substances 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- OXOKTPUZOHPXSA-UHFFFAOYSA-L manganese(2+);n-propyl-n-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide;dichloride Chemical class Cl[Mn]Cl.C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl.C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl.C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl.C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl OXOKTPUZOHPXSA-UHFFFAOYSA-L 0.000 description 3
- 244000052769 pathogen Species 0.000 description 3
- 230000001717 pathogenic effect Effects 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- 206010039509 Scab Diseases 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000205 computational method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000857 drug effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000035558 fertility Effects 0.000 description 2
- FQKUGOMFVDPBIZ-UHFFFAOYSA-N flusilazole Chemical compound C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 FQKUGOMFVDPBIZ-UHFFFAOYSA-N 0.000 description 2
- 230000036039 immunity Effects 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 241000235349 Ascomycota Species 0.000 description 1
- 208000031968 Cadaver Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005760 Difenoconazole Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- CFZLNRGUBAVQNO-UHFFFAOYSA-N N-(3,5-Dichlorophenyl)succinimide Chemical compound ClC1=CC(Cl)=CC(N2C(CCC2=O)=O)=C1 CFZLNRGUBAVQNO-UHFFFAOYSA-N 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000005842 Thiophanate-methyl Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IRUJZVNXZWPBMU-UHFFFAOYSA-N cartap Chemical compound NC(=O)SCC(N(C)C)CSC(N)=O IRUJZVNXZWPBMU-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- BQYJATMQXGBDHF-UHFFFAOYSA-N difenoconazole Chemical compound O1C(C)COC1(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)CN1N=CN=C1 BQYJATMQXGBDHF-UHFFFAOYSA-N 0.000 description 1
- FBOUIAKEJMZPQG-BLXFFLACSA-N diniconazole-M Chemical compound C1=NC=NN1/C([C@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-BLXFFLACSA-N 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- QGHREAKMXXNCOA-UHFFFAOYSA-N thiophanate-methyl Chemical compound COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC QGHREAKMXXNCOA-UHFFFAOYSA-N 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种含咪鲜胺和左旋α-松油醇的杀菌剂组合物及其生产方法，其特征在于有效成分咪鲜胺重量百分比为1％～50％，左旋α-松油醇重量百分比为1％～50％，余量为助剂。剂型为乳油、微乳剂或水乳剂。该组合物的优点在于复配后扩大了杀菌谱，而且具有明显的增效作用，显著降低了杀菌剂的使用量和使用次数，降低了成本，还将延缓病害的抗药性的产生，使其能够同时防治多种病害，可用于防治芒果炭疽病、稻瘟病和香蕉冠腐病等。同时左旋松油醇作为由天然可再生资源—松节油合成而来的单萜醇类，易于在环境中降解，符合绿色环保要求，此外本发明涉及的微乳剂、水乳剂则以水部分代替了有机溶剂，同样降低了环境污染。The invention discloses a fungicide composition containing prochloraz and L-α-terpineol and a production method thereof, which is characterized in that the active ingredient prochloraz is 1% to 50% by weight, and the weight percentage of L-α-terpineol is The percentage by weight is 1%-50%, and the balance is additives. The dosage form is emulsifiable oil, microemulsion or water emulsion. The advantage of the composition is that after compounding, the bactericidal spectrum is expanded, and it has obvious synergistic effect, which significantly reduces the amount and frequency of use of bactericides, reduces the cost, and also delays the emergence of drug resistance of diseases, making it It can prevent and control multiple diseases at the same time, and can be used to prevent and control mango anthracnose, rice blast and banana crown rot. Simultaneously L-terpineol, as the monoterpene alcohols synthesized by natural renewable resources---turpentine oil, is easy to degrade in the environment and meets the requirements of green environmental protection. In addition, the microemulsion and water emulsion involved in the present invention then replace the organic Solvents also reduce environmental pollution.
Description
Technical field
The present invention relates to a kind of composition pesticide, is the bactericide and the production method thereof of active ingredient with Prochloraz and left-handed alpha-terpineol particularly, and this composition pesticide can be applied to biocontrol of mango anthracnose, rice blast and banana crown rot.
Technical background
Terpineol also claims terpineol, α, β, 3 kinds of isomer of γ are arranged, wherein alpha-terpineol is the most common in nature, left-handed alpha-terpineol (English common name α-(L)-Terpineol), be by a synthetic compound of the applicant Chemical Industry Inst., Guangxi Zhuang Autonomous Region, (see Chinese patent application number: 03178548.4 applying date: 2003.07.16 title: the preparation method of left-handed alpha-terpineol), itself have good bactericidal activity, also have preferably simultaneously deodorize, moistening and infiltration capacity.Chemical Industry Inst., Guangxi Zhuang Autonomous Region has carried out a large amount of research to its biologically active, and the result shows that this compound can be used as disinfectant use in agriculture and uses.
Prochloraz claims to pounce on mould spirit again, (English common name prochloraz), chemical name: N-propyl group-N[α-(2,4, the 6-Trichlorophenoxy) ethyl]-1H-imidazoles-1-formamide, belong to the imidazoles bactericide, its sterilization mechanism mainly is to produce bactericidal action by the biosynthesis that suppresses mycosterol.Have characteristics such as protection of efficient, long-acting, tool and therapeutic action, the various crop disease that causes for sac fungi and imperfect fungus has special efficacy.The Lai Kaiping of the applicant Guangxi Chemical Inst., Wei Zhiming, Ye Yiqiang, Wang Guiying, Yang Hongquan are in " chemical industry technology and exploitation " 2007,36 (8) .-14-17 have delivered the article of " development of 50% propiconazole L-terpineol missible oil ", pass through screening test, the best proportioning of having determined 50% propiconazole L-terpineol missible oil is: propiconazole 20%, L-terpineol 30%, emulsifier 10%, solvent 40%.Through stability test, the every index of this missible oil meets the emulsifiable concentrates for agricultural chemicals standard.Field test results shows that 50% propiconazole L-terpineol missible oil can effectively be prevented and treated rice sheath blight disease under 1000～2000 times of conditions of dilution, and preventive effect is 66.2%～82.0%.Chinese patent also discloses the bactericide that some Prochlorazs and other compound are combined into, for example: 01123803.8, a kind of bactericide that contains diniconazole and prochloraz manganese salt; 200510094395.7, a kind of efficient bactericidal composite and application thereof that contains Prochloraz or its manganese salt and dimethachlon; 200610098368.1, contain the bactericide of thiophanate-methyl and Prochloraz; 200710035344.6, a kind of composition that contains prochloraz-manganese chloride complex and copper fungicide; 200810101943.8, a kind of composition that contains Prochloraz and cartap; 200910218740.1, a kind of bactericidal composition that contains prochloraz-manganese chloride complex and Difenoconazole.Shown Prochloraz to have bactericidal action preferably and be applied on the agricultural.
The price of Prochloraz is higher at present, and adds synergistic component, can improve its drug effect, reduce dosage, reduces the control cost.In the preventing and controlling of corps diseases, must be noted that to prevent that disease from developing immunity to drugs, be one of reason of developing immunity to drugs of disease and use single medicament for a long time.A kind of solution is that exploitation is new does not have the new active ingredient of cross resistance with existing product.But the development cost height of new active ingredient, the cycle is long, and is unable to catch up with the speed that disease produces resistance, and another kind of effective method is to carry out composite with different bactericide.Adopt similar and different bactericide compounded of the mode of action and demonstrate synergistic effect, promptly mixture is higher than in the mixture each component desired value of effect separately to the inhibitory action of pathogen growth, is the target of the bactericide compounded preparation of exploitation.
The open source literature report is not seen in composite research and the application of Prochloraz and left-handed alpha-terpineol at present.
Summary of the invention
The invention provides a kind of Prochloraz and the composite bactericide of left-handed alpha-terpineol, has synergistic function between this bactericide active ingredient, can widen bactericidal range, form a preventive effect height, hold and imitate the bactericide kind long, that use cost is low, this bactericide can be missible oil, microemulsion, aqueous emulsion.
Technical scheme of the present invention is as follows:
The microbicide compositions that contains Prochloraz and left-handed alpha-terpineol, it is characterized in that: this microbicide compositions is made up of active ingredient and auxiliary agent, active ingredient is Prochloraz (prochloraz) and left-handed alpha-terpineol (α-(L)-Terpineol), wherein the Prochloraz weight percentage is 1%～50%, left-handed alpha-terpineol weight percentage is for being 1%～50%, and all the other are auxiliary agents.
This microbicide compositions can be made missible oil, microemulsion or aqueous emulsion product as required.
Described auxiliary agent comprises one or more in surfactant, defoamer, antifreezing agent, thickener, solvent, cosolvent and the purified water.
In the described missible oil product, each component is formed and weight percentage is: Prochloraz 1%～50%, and left-handed alpha-terpineol 1%～50%, surfactant 1%～30%, all the other are solvent, each component sum is 100%.After each component mixing, stirring at normal temperatures obtains product.
In the described microemulsion product, each component is formed and weight percentage is: Prochloraz 1%～50%, left-handed alpha-terpineol 1%～50%, surfactant 1%～20%, antifreezing agent 0%～15%, cosolvent 0%～15%, solvent 1%～40%, purified water is supplemented to 100%.Prochloraz, left-handed alpha-terpineol, surfactant, antifreezing agent, cosolvent and solvent is even, slowly add the purified water of surplus at normal temperatures while stirring, obtain the product of homogeneous phase transparent.
In the described aqueous emulsion product, each component is formed and weight percentage is: Prochloraz 1%～50%, left-handed alpha-terpineol 1%～50%, surfactant 1%～20%, cosolvent 0%～15%, defoamer 0%～5%, antifreezing agent 0%～5%, thickener 0%～5%, solvent 1%～20%, purified water is supplemented to 100%.Prochloraz, left-handed alpha-terpineol, surfactant, solvent, cosolvent are mixed with the oil phase of homogeneous, defoamer, antifreeze, thickener and purified water are mixed, be mixed with the water of homogeneous.(rotating speed is under 1000～15000r/min) shearing conditions, and oil phase is added aqueous phase, keeps above-mentioned rotating speed then and shears 20～40min again, obtains product at normal temperature and homogenizer.
In the above-mentioned microbicide compositions product, described surfactant is wherein one or more of calcium dodecyl benzene sulfonate, alkyl poly glucoside, alkylaryl polyoxyethylene polyoxypropylene ether, phenethyl phenol polyethenoxy ether, dibenzyl xenyl APEO, fatty alcohol-polyoxyethylene ether and alkylphenol polyoxyethylene.
In the microbicide compositions of the present invention, described defoamer is one or more in silicone emulsion, isooctanol, polyether-modified silicon and the polyoxypropylene glycerin ether.
In the microbicide compositions product of the present invention, described antifreezing agent is one or more in ethylene glycol, propane diols, glycerine, sorbierite and the urea.
In the microbicide compositions product of the present invention, described thickener is a kind of in polyvinyl alcohol, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, xanthans and the alumina silicate.
In the microbicide compositions product of the present invention, described solvent is the single of esterification soybean oil, esterification cottonseed oil, toluene, dimethylbenzene, acetone, cyclohexanone, methyl alcohol, ethanol, diesel oil, kerosene, C10 aromatic solvent naphtha and purified water or the use that is mixed.
In the microbicide compositions product of the present invention, described cosolvent is one or more in oleic acid glyceryl ester, ethylene glycol, polyethylene glycol, propane diols, glycerine and the n-butanol.
Of the present invention is the bactericide production method of active ingredient with Prochloraz and left-handed alpha-terpineol:
Press raw material weight percentage,, add surfactant, solvent on demand successively, be stirred to homogeneous phase liquid at normal temperatures, obtain the missible oil product Prochloraz, left-handed alpha-terpineol.
Press raw material weight percentage, Prochloraz, left-handed alpha-terpineol, surfactant, antifreezing agent, cosolvent and solvent is even, slowly add the purified water of surplus at normal temperatures while stirring, obtain the microemulsion product of homogeneous phase transparent.
Press raw material weight percentage, Prochloraz, left-handed alpha-terpineol, surfactant, solvent, cosolvent are mixed with the oil phase of homogeneous, defoamer, antifreeze, thickener and purified water are mixed, be mixed with the water of homogeneous.(rotating speed is under 1000～15000r/min) shearing conditions, and oil phase is added aqueous phase, keeps above-mentioned rotating speed then and shears 20～40min again, obtains the aqueous emulsion product at normal temperature and homogenizer.
Microbicide compositions provided by the present invention can be applied to biocontrol of mango anthracnose, rice blast and banana crown rot etc.
The present invention has following advantage:
(1) the present invention makes after composite the activity of mixture obtain increasing, and has obvious synergistic effect, has remedied the deficiency of agricultural chemicals list agent, has significantly reduced the usage amount and the access times of bactericide, reduces cost.
(2) the present invention has enlarged the bactericidal activity scope after composite, can prevent and treat multiple diseases simultaneously.
(3) the present invention makes pathogen be difficult to eliminate simultaneously the influence of two kinds of different bactericide to it after composite, delays that pesticide resistance is individual in the pathogen produces.
(4) the L-terpineol conduct is by natural reproducible resource---the monoterpene alcohols that turpentine oil is synthetic and next, be easy in environment, degrade, and meet environment protection requirement.Microemulsion, the aqueous emulsion that the present invention relates to have then replaced organic solvent with water section, have reduced environmental pollution equally.
Embodiment
The invention will be further described below in conjunction with embodiment, but content of the present invention is not limited thereto.
Embodiment 1 (the left-handed alpha-terpineol missible oil of 20% Prochloraz):
(1) raw material proportioning:
By weight percentage, Prochloraz 15%, left-handed alpha-terpineol 5%, calcium dodecyl benzene sulfonate 4%, alkylphenol polyoxyethylene 2%, dibenzyl xenyl APEO 4%, dimethylbenzene 30%, the esterification soybean oil is supplemented to 100%.
(2) preparation method:
With Prochloraz, left-handed alpha-terpineol, calcium dodecyl benzene sulfonate, alkylphenol polyoxyethylene, dibenzyl xenyl APEO and dimethylbenzene, add successively and be stirred to homogeneous phase liquid in the esterification soybean oil, obtain active constituent content and be 20% composition missible oil.
Embodiment 2 (the left-handed alpha-terpineol missible oil of 25% Prochloraz):
(1) raw material proportioning:
By weight percentage, Prochloraz 20%, left-handed alpha-terpineol 5%, calcium dodecyl benzene sulfonate 4%, alkylphenol polyoxyethylene 6%, dimethylbenzene is supplemented to 100%.
(2) preparation method:
With Prochloraz, left-handed alpha-terpineol, calcium dodecyl benzene sulfonate and alkylphenol polyoxyethylene, add successively and be stirred to homogeneous phase liquid in the dimethylbenzene, obtain active constituent content and be 25% composition missible oil.
Embodiment 3 (the left-handed alpha-terpineol missible oil of 50% Prochloraz):
(1) raw material proportioning:
By weight percentage, Prochloraz 40%, left-handed alpha-terpineol 10%, calcium dodecyl benzene sulfonate 4%, phenethyl phenol polyethenoxy ether 6%, acetone 20%, toluene is supplemented to 100%.
(2) preparation method:
With Prochloraz, left-handed alpha-terpineol, calcium dodecyl benzene sulfonate, phenethyl phenol polyethenoxy ether and acetone, add successively and be stirred to homogeneous phase liquid in the toluene, obtain active constituent content and be 50% composition missible oil.
Embodiment 4 (the left-handed alpha-terpineol missible oil of 55% Prochloraz):
(1) raw material proportioning:
By weight percentage, Prochloraz 15%, left-handed alpha-terpineol 40%, calcium dodecyl benzene sulfonate 5%, alkylaryl polyoxyethylene polyoxypropylene ether 7%, the C10 aromatic solvent naphtha is supplemented to 100%.
(2) preparation method:
With Prochloraz, left-handed alpha-terpineol, calcium dodecyl benzene sulfonate and alkylaryl polyoxyethylene polyoxypropylene ether, add successively and be stirred to homogeneous phase liquid in the C10 aromatic solvent naphtha, obtain active constituent content and be 55% composition missible oil.
Embodiment 5 (the left-handed alpha-terpineol microemulsion of 20% Prochloraz):
(1) raw material proportioning:
By weight percentage, Prochloraz 15%, left-handed alpha-terpineol 5%, ethanol 18%, calcium dodecyl benzene sulfonate 3%, alkyl poly glucoside 9%, ethylene glycol 3%, purified water is supplemented to 100%.
(2) preparation method:
With Prochloraz, left-handed alpha-terpineol, ethanol abundant stirring and dissolving in reaction vessel, add calcium dodecyl benzene sulfonate, alkyl poly glucoside, ethylene glycol more successively and mix, after slowly add the purified water of surplus while stirring, mix to stir 1 hour, and obtained active constituent content and be 20% composite microemulsion.
Embodiment 6 (the left-handed alpha-terpineol microemulsion of 30% Prochloraz):
(1) raw material proportioning:
By weight percentage, Prochloraz 20%, left-handed alpha-terpineol 10%, cyclohexanone 20%, calcium dodecyl benzene sulfonate 4%, alkylaryl polyoxyethylene polyoxypropylene ether 12%, ethylene glycol 3%, propane diols 2%, purified water is supplemented to 100%.
(2) preparation method:
With Prochloraz, left-handed alpha-terpineol, cyclohexanone abundant stirring and dissolving in reaction vessel, add calcium dodecyl benzene sulfonate, alkylaryl polyoxyethylene polyoxypropylene ether, ethylene glycol, propane diols more successively and mix, after slowly add the purified water of surplus while stirring, mix to stir 1 hour, and obtained active constituent content and be 30% composite microemulsion.
Embodiment 7 (the left-handed alpha-terpineol aqueous emulsion of 30% Prochloraz):
(1) raw material proportioning:
By weight percentage, Prochloraz 25%, left-handed alpha-terpineol 5%, calcium dodecyl benzene sulfonate 3%, alkylphenol polyoxyethylene 7%, dimethylbenzene 25%, isooctanol 0.5%, polyoxypropylene glycerin ether 0.5%, ethylene glycol 1%, polyvinyl alcohol 0.5%, purified water is supplemented to 100%.
(2) preparation method:
With Prochloraz, left-handed alpha-terpineol, calcium dodecyl benzene sulfonate, alkylphenol polyoxyethylene, dimethylbenzene abundant stirring and dissolving in container, be mixed with the oil phase of homogeneous.Isooctanol, polyoxypropylene glycerin ether, ethylene glycol, polyethylene alcohol and water are mixed in container, be mixed with the water of homogeneous.Normal temperature and homogenizer (rotating speed is under 4000～5000r/min) the high speed shear conditions, and oil phase is slowly added the aqueous phase of formula ratio, add finish after, continue to keep above-mentioned rotating speed cutting 30min, promptly obtain active constituent content and be 30% composition aqueous emulsion.
Embodiment 8 (containing Prochloraz and left-handed alpha-terpineol microbicide compositions field control effectiveness test) to mango anthracnose
(1) test medicine
Reagent agent is the left-handed alpha-terpineol missible oil of 25% Prochloraz among the embodiment 2, establishes 1000 times, 1500 times, 2000 times 3 concentration and handles; The contrast medicament is 25% Prochloraz missible oil and 25% left-handed alpha-terpineol missible oil.Two contrast medicaments are 1000 times of 1 concentration and handle; Establishing clear water in addition handles.
(2) subjects and environmental condition
Controlling object is a mango anthracnose.Middle fertility experimental field, the mango kind is red awns, the age of tree is 5 years.The orchard was the paddy field originally, and physical features is smooth, and the householder plays the furrow plantation, every furrow single file plantation, and planting density is every mu of about 40 strains.Each phase rich water quality management of mango, control of insect measure belong to local medium level.
(3) arrange the sub-district
Arrange the sub-district by distinguishing group of methods at random.4 repetitions are established in every processing, 1 sub-district of every repetition, every sub-district be 3 strains for examination mango strain number, amount to for 72 strains of examination mango.
(4) application method
Begin dispenser from the mango young fruit period, spraying times is 3 times, each 14 days at interval.(Taizhou city strange power farm chemical apparatus of road and bridge factory produces the spraying equipment that uses, model: the 3WBS-15 type) as the backpack hand sprayer.Take the dispenser of foliar spray method, evenly to squirt mango blade and fruit degree of being.
(5) investigation method, time and number of times
Random searching 2 strains of every sub-district, every strain press East, West, South, North, in 5 samplings, every 10 of fruit of investigation is investigated 100 of fruits altogether.Sick fruit stage division:
0 grade---no scab;
1 grade---needle-like brown spot is less than 5;
3 grades---needle-like brown spot is less than 6～15;
5 grades---needle-like brown spot is less than 16～25;
7 grades---needle-like brown spot is more than 25, and spot links to each other;
9 grades---whole fruit is met personally scab, has red point-like thing to occur.
Carry out the investigation of 4 state of an illness altogether: investigation for the first time is morbidity radix investigation before the medicine, after the 2nd time and the 3rd dispenser 14 days each investigate once.
(6) drug effect computational methods
This pilot survey disease index (referring to) and control efficiency (hereinafter to be referred as preventive effect) hereinafter to be referred as disease, its computational methods are as follows:
The results are shown in Table 2.
The left-handed alpha-terpineol missible oil of table 2:25% Prochloraz is to the preventive effect of mango anthracnose
As seen from the table, the 2nd dispenser " Invest, Then Investigate ", 1000 times of preventive effects to mango anthracnose of the left-handed alpha-terpineol missible oil of 25% Prochloraz dilution are 80.70%, be higher than 25% Flusilazole missible oil under the same concentrations 75.32% and 25% left-handed alpha-terpineol missible oil 37.99%.The 3rd dispenser " Invest, Then Investigate ", 1000 times of preventive effects to mango anthracnose of the left-handed alpha-terpineol missible oil dilution of 25% Prochloraz are 86.41%, also be higher than 25% Flusilazole missible oil under the same concentrations 79.61% and 25% left-handed alpha-terpineol missible oil 42.12%, illustrating that Prochloraz and left-handed alpha-terpineol are composite has a good synergistic effect.
Embodiment 9 (containing Prochloraz and left-handed alpha-terpineol microbicide compositions field control effectiveness test) to rice blast, banana crown rot
(1) test medicine
Reagent agent is the left-handed alpha-terpineol missible oil of 25% Prochloraz among the embodiment 2, establishes 1000 times, 1500 times, 2000 times 3 concentration and handles; The contrast medicament is 25% Prochloraz missible oil and 25% left-handed alpha-terpineol missible oil.Two contrast medicaments are 1000 times of 1 concentration and handle; Establishing clear water in addition handles.All are handled and all establish 4 repetitions.
(2) subjects and test site
Rice blast control test is carried out in Nanning city Xingning District Wu Tang town; The banana crown rot is carried out in Xixiangtang District Nanjing, Nanning city town.Middle fertility experimental field, the cultivation condition unanimity of all experimental plots, and meet the agricultural practice of local science.
(3) result
Final the survey showed that, and 1000 times of preventive effects to rice blast, banana crown rot of the left-handed alpha-terpineol missible oil dilution of 25% Prochloraz are respectively 91.50% and 76.75%; Contrast medicament 25% Prochloraz missible oil is respectively 85.43% and 75.23% to the preventive effect of rice blast, banana crown rot; Contrast medicament 25% left-handed alpha-terpineol missible oil is respectively 63.50% and 49.28% to the preventive effect of rice blast, banana crown rot; From result of the test, microbicide compositions of the present invention is higher than the agent of former agricultural chemicals list respectively to the preventive effect to rice blast, banana crown rot, and explanation Prochloraz and left-handed alpha-terpineol be composite good synergistic effect.
Claims (8)
1. microbicide compositions that contains Prochloraz and left-handed alpha-terpineol, it is characterized in that: this microbicide compositions is made up of active ingredient and auxiliary agent, active ingredient is Prochloraz (prochloraz) and left-handed alpha-terpineol (α-(L)-Terpineol), wherein the Prochloraz weight percentage is 1%～50%, left-handed alpha-terpineol weight percentage is 1%～50%, and all the other are auxiliary agents.
2. according to the described microbicide compositions that contains Prochloraz and left-handed alpha-terpineol of claim 1, it is characterized in that: described composition comprises missible oil, microemulsion or the aqueous emulsion of being made by active ingredient and auxiliary agent.
3. according to claim 1 and the 2 described microbicide compositions that contain Prochloraz and left-handed alpha-terpineol, it is characterized in that: described auxiliary agent comprises one or more in surfactant, defoamer, antifreezing agent, thickener, solvent, cosolvent and the purified water.
4. as claim 1 and the 2 described production methods that contain the bactericide product of Prochloraz and left-handed alpha-terpineol, it is characterized in that: in the described missible oil product, each component is formed and weight percentage is: Prochloraz 1%～50%, left-handed alpha-terpineol 1%～50%, surfactant 1%～30%, all the other are solvent, and each component sum is 100%.After each component mixing, stirring at normal temperatures obtains product.
5. as claim 1 and the 2 described production methods that contain the bactericide product of Prochloraz and left-handed alpha-terpineol, it is characterized in that: in the described microemulsion product, each component is formed and weight percentage is: Prochloraz 1%～50%, left-handed alpha-terpineol 1%～50%, surfactant 1%～20%, antifreezing agent 0%～15%, cosolvent 0%～15%, solvent 1%～40%, purified water is supplemented to 100%.Prochloraz, left-handed alpha-terpineol, surfactant, antifreezing agent, cosolvent and solvent is even, slowly add the purified water of surplus at normal temperatures while stirring, obtain the product of homogeneous phase transparent.
6. as claim 1 and the 2 described microbicide compositions that contain Prochloraz and left-handed alpha-terpineol, it is characterized in that: in the described aqueous emulsion product, each component is formed and weight percentage is: Prochloraz 1%～50%, left-handed alpha-terpineol 1%～50%, surfactant 1%～20%, cosolvent 0%～15%, defoamer 0%～5%, antifreezing agent 0%～5%, thickener 0%～5%, solvent 1%～20%, purified water is supplemented to 100%.Prochloraz, left-handed alpha-terpineol, surfactant, solvent, cosolvent are mixed with the oil phase of homogeneous, defoamer, antifreeze, thickener and purified water are mixed, be mixed with the water of homogeneous.(rotating speed is under 1000～15000r/min) shearing conditions, and oil phase is added aqueous phase, keeps above-mentioned rotating speed then and shears 20～40min again, obtains product at normal temperature and homogenizer.
7. the microbicide compositions that contains Prochloraz and left-handed alpha-terpineol as claimed in claim 3 is characterized in that: described surfactant is wherein one or more of calcium dodecyl benzene sulfonate, alkyl poly glucoside, alkylaryl polyoxyethylene polyoxypropylene ether, phenethyl phenol polyethenoxy ether, dibenzyl xenyl APEO, fatty alcohol-polyoxyethylene ether and alkylphenol polyoxyethylene;
Described defoamer is one or more in isooctanol, silicone emulsion and the polyoxypropylene glycerin ether;
Described antifreezing agent is one or more in ethylene glycol, propane diols, glycerine, sorbierite and the urea;
Described thickener is one or more in polyvinyl alcohol, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, xanthans and the alumina silicate;
Described solvent is the single of esterification soybean oil, esterification cottonseed oil, toluene, dimethylbenzene, acetone, cyclohexanone, methyl alcohol, ethanol, diesel oil, kerosene, C10 aromatic solvent naphtha and purified water or the use that is mixed;
Described cosolvent is one or more in oleic acid glyceryl ester, ethylene glycol, polyethylene glycol, propane diols, glycerine and the n-butanol.
As claim 1 and the 2 described microbicide compositions that contain Prochloraz and left-handed alpha-terpineol in the purposes aspect the agricultural chemicals of preparation biocontrol of mango anthracnose, rice blast and banana crown rot etc.
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Cited By (4)
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| CN103650835A (en) * | 2013-09-30 | 2014-03-26 | 横县生产力促进中心 | A kind of planting method of organic jasmine |
| CN110691515A (en) * | 2017-06-07 | 2020-01-14 | 韩国原子力硏究院 | Composition for controlling plant diseases comprising limonene derivative as active ingredient |
| CN111466401A (en) * | 2020-05-22 | 2020-07-31 | 广西壮族自治区农业科学院植物保护研究所 | Bactericidal composition and application thereof |
| CN111499510A (en) * | 2020-04-21 | 2020-08-07 | 成都新朝阳作物科学股份有限公司 | Compound and preparation method and application thereof |
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| JP2007186496A (en) * | 2005-12-12 | 2007-07-26 | Sumitomo Chemical Co Ltd | Microcapsules containing solid agrochemical active compounds |
| CN101530097A (en) * | 2008-03-14 | 2009-09-16 | 北京绿色农华植保科技有限责任公司 | Compound containing prochloraz and cartap hydrochloride |
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| JP2007186496A (en) * | 2005-12-12 | 2007-07-26 | Sumitomo Chemical Co Ltd | Microcapsules containing solid agrochemical active compounds |
| CN101530097A (en) * | 2008-03-14 | 2009-09-16 | 北京绿色农华植保科技有限责任公司 | Compound containing prochloraz and cartap hydrochloride |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103650835A (en) * | 2013-09-30 | 2014-03-26 | 横县生产力促进中心 | A kind of planting method of organic jasmine |
| CN103650835B (en) * | 2013-09-30 | 2015-08-26 | 横县生产力促进中心 | Planting method of organic jasmine |
| CN110691515A (en) * | 2017-06-07 | 2020-01-14 | 韩国原子力硏究院 | Composition for controlling plant diseases comprising limonene derivative as active ingredient |
| JP2020522561A (en) * | 2017-06-07 | 2020-07-30 | コリア アトミック エナジー リサーチ インスティテュートＫｏｒｅａ Ａｔｏｍｉｃ Ｅｎｅｒｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Composition for controlling plant diseases containing a limonene derivative as an active ingredient |
| US11213029B2 (en) | 2017-06-07 | 2022-01-04 | Korea Atomic Energy Research Institute | Composition for plant disease control comprising limonene derivatives as active ingredients |
| CN111499510A (en) * | 2020-04-21 | 2020-08-07 | 成都新朝阳作物科学股份有限公司 | Compound and preparation method and application thereof |
| CN111499510B (en) * | 2020-04-21 | 2023-03-31 | 成都新朝阳作物科学股份有限公司 | Compound and preparation method and application thereof |
| CN111466401A (en) * | 2020-05-22 | 2020-07-31 | 广西壮族自治区农业科学院植物保护研究所 | Bactericidal composition and application thereof |
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