WO2020134105A1 - 丙硫菌唑可分散油悬浮剂 - Google Patents
丙硫菌唑可分散油悬浮剂 Download PDFInfo
- Publication number
- WO2020134105A1 WO2020134105A1 PCT/CN2019/100177 CN2019100177W WO2020134105A1 WO 2020134105 A1 WO2020134105 A1 WO 2020134105A1 CN 2019100177 W CN2019100177 W CN 2019100177W WO 2020134105 A1 WO2020134105 A1 WO 2020134105A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- prothioconazole
- oil
- dispersible oil
- dispersible
- suspension agent
- Prior art date
Links
- MNHVNIJQQRJYDH-UHFFFAOYSA-N 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1=CNC(=S)N1CC(C1(Cl)CC1)(O)CC1=CC=CC=C1Cl MNHVNIJQQRJYDH-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000005825 Prothioconazole Substances 0.000 title claims abstract description 69
- 239000012053 oil suspension Substances 0.000 title claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003921 oil Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 239000013530 defoamer Substances 0.000 claims abstract description 9
- 239000000440 bentonite Substances 0.000 claims description 21
- 229910000278 bentonite Inorganic materials 0.000 claims description 21
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 21
- 235000019198 oils Nutrition 0.000 claims description 20
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 20
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- 235000012424 soybean oil Nutrition 0.000 claims description 18
- 239000003549 soybean oil Substances 0.000 claims description 18
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 17
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 16
- 239000002480 mineral oil Substances 0.000 claims description 16
- 235000010446 mineral oil Nutrition 0.000 claims description 16
- 229940073769 methyl oleate Drugs 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 150000007942 carboxylates Chemical class 0.000 claims description 10
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 8
- -1 alkyl phenol formaldehyde resin Chemical compound 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000375 suspending agent Substances 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 125000005504 styryl group Chemical group 0.000 claims 1
- 125000005457 triglyceride group Chemical group 0.000 claims 1
- 239000000725 suspension Substances 0.000 abstract description 7
- 229910021485 fumed silica Inorganic materials 0.000 abstract 1
- 229920005646 polycarboxylate Polymers 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 12
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 12
- 239000004576 sand Substances 0.000 description 10
- 239000003814 drug Substances 0.000 description 8
- 229940079593 drug Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 201000010099 disease Diseases 0.000 description 7
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000009472 formulation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 241001558929 Sclerotium <basidiomycota> Species 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 3
- JBPBZQRUTGSRAC-UHFFFAOYSA-N 1-benzyl-4-(4-benzylphenyl)benzene Chemical group C=1C=C(C=2C=CC(CC=3C=CC=CC=3)=CC=2)C=CC=1CC1=CC=CC=C1 JBPBZQRUTGSRAC-UHFFFAOYSA-N 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 2
- 240000005979 Hordeum vulgare Species 0.000 description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000238578 Daphnia Species 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 239000005586 Nicosulfuron Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 241000256618 Trichogramma Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 241001233061 earthworms Species 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 230000008686 ergosterol biosynthesis Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 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 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- QPDUQKTYZRXRBC-UHFFFAOYSA-N triazole-4-thione Chemical compound S=C1C=NN=N1 QPDUQKTYZRXRBC-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
- 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
- A01N25/30—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 characterised by the surfactants
Definitions
- the invention relates to the technical field of bactericides, in particular to a prothioconazole dispersible oil suspension agent.
- Prothioconazole is a new broad-spectrum triazolethione fungicide discovered, developed and produced by Bayer CropScience.
- Prothioconazole is a sterol demethylation (ergosterol biosynthesis) inhibitor, which not only has good systemic action, excellent protection, treatment and eradication activity, but also has a long duration.
- a large number of field efficacy test results show that prothioconazole is safe for crops, effective in preventing and curing diseases, and has a significant increase in yield.
- Prothioconazole is mainly used to control diseases on crops such as wheat, barley, rape, peanuts, rice, bean crops, sugar beet and field vegetables.
- prothioconazole Compared with triazole fungicides, prothioconazole has a broader bactericidal spectrum. It has a good control effect on almost all wheat diseases, such as powdery mildew, sheath blight, Fusarium wilt, leaf spot, rust, sclerotium, net blotch, moire, etc. on wheat and barley; Control soil-borne diseases of rape and peanut, such as sclerotium disease, and major foliar diseases such as gray mold, black spot, brown spot, black shin disease, sclerotium and rust.
- wheat diseases such as powdery mildew, sheath blight, Fusarium wilt, leaf spot, rust, sclerotium, net blotch, moire, etc. on wheat and barley
- Control soil-borne diseases of rape and peanut such as sclerotium disease, and major foliar diseases such as gray mold, black spot, brown spot, black shin disease
- prothioconazole has no environmental risk concerns, that is, prothioconazole is safe for bees, birds, fish, silkworms, algae, daphnia, earthworms, and natural enemy Trichogramma.
- Dispersible oil suspending agent is one or more pesticide active ingredients (one of which is solid original drug) forming a highly dispersed and stable suspension system in a non-aqueous dispersion medium.
- Advantages vegetable oil, mineral oil, etc., no organic solvents, low toxicity, easy degradation, environmentally friendly; high flash point, safer than emulsified oil; vegetable oil and mineral oil, methyl oleate, etc.
- the technical problem to be solved by the present invention is to provide a prothioconazole dispersible oil suspension agent with high suspension stability.
- the present invention provides a prothioconazole dispersible oil suspension agent, which is calculated according to the weight percentage, including:
- the weight percentage content of prothioconazole is 10% to 40%, further preferably 10% to 30%.
- the emulsifier is preferably any one of triglyceride polyoxyethylene ether, dibenzyl biphenyl polyoxyethylene ether, styryl phenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether One or more.
- the weight percentage content of the emulsifier is 2% to 10%, further preferably 8%.
- the polymeric carboxylate dispersant is preferably sodium polyacrylate.
- the weight percent content of the polymeric carboxylate dispersant is 2%-8%, more preferably 5%.
- the present invention uses a polymeric carboxylate dispersant, which improves the dispersibility of prothioconazole in oil solvents compared to traditional dispersants. It has good compatibility with oil solvents, large charge density, moderate molecular weight, and a comb structure. It can effectively wrap the surface of the original drug particles, avoiding the situation that the product is prone to sedimentation during storage.
- the weight percentage content of the viscosity modifier is 0.5% to 6%, further preferably 1.5% to 2.5%.
- the viscosity modifier is a mixture of organic bentonite and meteorological silica.
- the mass ratio of the organic bentonite and meteorological silica is (1 to 3): (3 to 1), further It is preferably 1:3.
- the invention adopts a mixture of organic bentonite and meteorological white carbon as the viscosity adjuster of prothioconazole dispersible oil suspension agent, wherein the organic bentonite can adjust the viscosity of the system so that the system has thixotropy and is in a suspended state.
- Meteorological white carbon black is all nano-silica, its particle size is 10-20nm, it has ultra-high surface area and very strong adsorption force. After mixing with organic bentonite, it improves its thixotropic performance and prevents the preparation from agglomerating. It has very good affinity and physical and chemical stability, which improves the stability of suspending agent at low temperature and high temperature. It is beneficial to the action of viscosity modifier and prothioconazole and improve its stability.
- the defoamer is preferably silicone.
- the weight percentage content of the defoaming agent is 0.1% to 1%, further preferably 0.5%.
- the prothioconazole dispersible oil suspension agent also includes the balance of oil.
- the oil is a mixture of modified soybean oil, methyl oleate, and mineral oil.
- the mass ratio of the modified soybean oil, methyl oleate and mineral oil is preferably (1 to 3): (1 to 6): (1 to 2), more preferably 1:3 to 6:1.
- the prothioconazole dispersible oil suspension agent of the present invention uses a mixed oil solvent of modified soybean oil, methyl oleate, and mineral oil, so that it exhibits a stronger permeability on the crop surface than the water solvent, and reduces the effective Loss of ingredients has obvious synergistic effect.
- the preparation method of the prothioconazole dispersible oil suspension agent is not particularly limited, and may be a preparation method of a dispersible oil suspension agent well known to those skilled in the art.
- the invention provides a preparation method of the above prothioconazole dispersible oil suspension agent, comprising the following steps:
- Prothioconazole, emulsifier, polymeric carboxylate dispersant, viscosity adjuster, defoamer, and oil are mixed evenly, and then ground to obtain prothioconazole dispersible oil suspension.
- the polishing time is preferably 1 to 2 hours.
- the prothioconazole dispersible oil suspension is prepared according to the following method:
- prothioconazole original drug emulsifier, polymeric carboxylate dispersant, defoamer, organic bentonite, meteorological white carbon and modified soybean oil, methyl oleate, mineral oil
- the mixing kettle Under cutting and stirring, the materials are fully mixed and evenly mixed, the mixture is driven into a sand mill for grinding, and sand milled for 1 to 2 hours to prepare a prothioconazole dispersible oil suspension agent.
- the present invention provides a prothioconazole dispersible oil suspension agent, calculated according to weight percentage, including: prothioconazole 10%-30%, emulsifier 8%, polymeric carboxylate dispersion Agent 5%, viscosity modifier 4%, defoamer 0.5%, the balance is oil; the viscosity modifier is a mixture of organic bentonite and meteorological silica.
- the prothioconazole dispersible oil suspension agent provided by the present invention has stable performance.
- the prothioconazole dispersible oil suspension agent of the present invention reduces the use of organic solvents and is more environmentally friendly, safe, safe for storage, transportation and use , And environmentally friendly, in line with the development direction of today's pesticide formulations, compared to water suspension formulations, the prothioconazole dispersible oil suspension product of the present invention has more stable suspension performance, long validity period, and no serious precipitation of water suspension products. The phenomenon.
- the experimental results prove that the suspending agent not only has high suspension stability, but also meets the needs of different water quality areas, high altitude areas, low temperature areas, and high temperature areas near the equator, and also reduces the impact of organic solvents on the environment.
- prothioconazole dispersible oil suspension agent provided by the present invention will be described in detail below in conjunction with examples.
- prothioconazole original drug triglyceride polyoxyethylene ether, sodium polyacrylate, silicone, organic bentonite, meteorological silica, modified soybean oil, methyl oleate, minerals
- the mixture is driven into a sand mill for grinding, sand milled for 1 to 2 hours, to obtain prothioconazole dispersible oil suspension.
- prothioconazole original drug dibenzyl biphenyl polyoxyethylene ether, sodium polyacrylate, silicone, organic bentonite, meteorological white carbon and modified soybean oil, methyl oleate, Mineral oil, under high shear agitation, make the materials fully mixed evenly, the mixture is driven into a sand mill for grinding, sand milled for 1 to 2 hours to obtain prothioconazole dispersible oil suspension.
- the formulation is as follows:
- the formulation is as follows:
- the formulation is as follows:
- the formulation is as follows:
- the prothioconazole dispersible oil suspension agent prepared by the present invention has excellent wetting performance, high suspension rate, and good storage stability, and has strong strength at -4°C and 54°C Stability to meet the needs of low temperature and high temperature areas.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
提供一种丙硫菌唑可分散油悬浮剂，按照重量百分数计算，包括：丙硫菌唑10%~40%、乳化剂2%~10%、聚合羧酸盐分散剂2%~8%、黏度调节剂0.5%~6%、消泡剂0.1%~1%，余量为油；所述黏度调节剂为有机膨润土和气相白炭黑组成的混合物。该丙硫菌唑可分散油悬浮剂悬浮率高，贮存稳定性好，满足高温地区和低温地区的需要。
Description
本申请要求于2018年12月26日提交中国专利局、申请号为201811598012.3、发明名称为“丙硫菌唑可分散油悬浮剂”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
本发明涉及杀菌剂技术领域，尤其涉及一种丙硫菌唑可分散油悬浮剂。
丙硫菌唑，是由拜耳作物科学公司发现、开发并生产的新型广谱三唑硫酮类杀菌剂。丙硫菌唑为甾醇脱甲基化(麦角甾醇生物合成)抑制剂，其不仅具有良好的内吸作用，优异的保护、治疗和铲除活性，而且持效期长。大量的田间药效试验结果表明：丙硫菌唑对作物安全性好，防病治病效果好，而且增产明显。丙硫菌唑主要用于防治小麦、大麦、油菜、花生、水稻、豆类作物、甜菜和大田蔬菜等作物上的病害。同三唑类杀菌剂相比，丙硫菌唑具有更广泛的杀菌谱。几乎对所有麦类病害具有很好的防治效果，如小麦和大麦上的白粉病、纹枯病、枯萎病、叶斑病、锈病、菌核病、网斑病、云纹病等；还能防治油菜和花生的土传病害，如菌核病，以及主要叶面病害，如灰霉病、黑斑病、褐斑病、黑胫病、菌核病和锈病等。而且，更难能可贵的是丙硫菌唑无环境风险关注点，即丙硫菌唑对蜂、鸟、鱼、蚕、水藻、水蚤、蚯蚓、天敌赤眼蜂等安全。
可分散油悬浮剂，英语简称为OD，是一种或一种以上的农药有效成分(其中一种为固体原药)在非水系分散介质中形成高分散、稳定的悬浮体系。优点：用植物油、矿物油等，不用有机溶剂，毒性低、易降解，对环境友好；闪点高，比乳油更安全；植物油和矿物油、油酸甲酯等可以提高制剂药效；对一些易水解的固体原药尤其适合(比如烟嘧磺隆)；在缺水的干旱地区或者飞机喷洒施药情况下，希望少用、甚至不用水，或者用超低容量喷雾，也可直接用油悬浮剂(要符合ULV标准)喷雾更为经济方便。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种丙硫菌唑可分散油悬浮剂，具有较高的悬浮稳定性。
为解决以上技术问题，本发明提供了一种丙硫菌唑可分散油悬浮剂，按照重量百分数计算，包括：
丙硫菌唑10％～40％、乳化剂2％～10％、聚合羧酸盐分散剂2％～8％、黏度调节剂0.5％～6％、消泡剂0.1％～1％，余量为油；所述黏度调节剂为有机膨润土和气象白炭黑组成的混合物。
所述可分散油悬浮剂中，丙硫菌唑的重量百分数含量为10％～40％，进一步优选为10％～30％。
所述乳化剂优选为三篦酸甘油脂聚氧乙烯醚、二苄基联苯基聚氧乙烯醚、苯乙烯基苯基聚氧乙烯醚、烷基酚甲醛树脂聚氧乙烯醚中的任意一种或多种。
所述乳化剂的重量百分数含量为2％～10％，进一步优选为8％。
所述聚合羧酸盐分散剂优选为聚丙烯酸钠。
所述聚合羧酸盐分散剂的重量百分数含量为2％～8％，进一步优选为5％。
本发明使用聚合羧酸盐分散剂，相比传统分散剂提高了丙硫菌唑在油溶剂中的分散性，其与油溶剂的相溶性好，电荷密度大，分子量适中，呈梳型结构，可以有效的包裹原药颗粒表面，避免了产品在储存过程中容易发生沉降的情况。
所述黏度调节剂的重量百分数含量为0.5％～6％，进一步优选为1.5％～2.5％。
本发明中，所述黏度调节剂为有机膨润土和气象白炭黑组成的混合物，优选的，所述有机膨润土和气象白炭黑的质量比为(1～3):(3～1)，进一步优选为1：3。
本发明采用有机膨润土和气象白炭黑的混合物作为丙硫菌唑可分散油悬浮剂的黏度调节剂，其中，有机膨润土可以调节体系黏度，使体系具有触变性，呈悬浮状态。气象白炭黑全部是纳米二氧化硅，其粒径在10～20nm，具有超高的表面积和非常强的吸附力，其与有机膨润土混合后，提高了其触变性能，防止制剂结块，有非常好的亲和性以及物理化学稳定性，提高了悬浮剂在低温、高温的稳定性。有利于黏度调节剂与丙硫菌唑原药作用，提高其稳定性。
所述消泡剂优选为有机硅。
所述消泡剂的重量百分数含量为0.1％～1％，进一步优选为0.5％。
所述丙硫菌唑可分散油悬浮剂还包括余量的油。
优选的，所述油为改性大豆油、油酸甲酯、矿物油的混合物。
所述改性大豆油、油酸甲酯和矿物油的质量比优选为(1～3):(1～6):(1～2)，进一步优选为1：3～6：1。
本发明的丙硫菌唑可分散油悬浮剂使用了改性大豆油、油酸甲酯、矿物油的混合油溶剂，使其在作物面展着渗透性比水溶剂的效果要强，减少了有效成分流失，有明显增效作用。
本发明对所述丙硫菌唑可分散油悬浮剂的制备方法并无特殊限定，可以为本领域技术人员熟知的可分散油悬浮剂的制备方法。
本发明提供了上述丙硫菌唑可分散油悬浮剂的制备方法，包括以下步骤：
将丙硫菌唑、乳化剂、聚合羧酸盐分散剂、黏度调节剂、消泡剂，油混合均匀，然后研磨，得到丙硫菌唑可分散油悬浮剂。
本发明优选的，所述研磨的时间为1～2h。
上述乳化剂、聚合羧酸盐分散剂、黏度调节剂、消泡剂，油的具体种类和含量同上，在此不再赘述。
在本发明的一些具体实施例中，所述丙硫菌唑可分散油悬浮剂按照以下方法制备：
向混合釜内加入丙硫菌唑原药、乳化剂、聚合羧酸盐分散剂、消泡剂、有机膨润土、气象白炭黑和改性大豆油、油酸甲酯、矿物油，在高剪切搅拌下，使物料充分混合均匀，将混合物料打入砂磨机中研磨，砂磨1～2h，制备得到丙硫菌唑可分散油悬浮剂。
与现有技术相比，本发明提供了一种丙硫菌唑可分散油悬浮剂，按照重量百分数计算，包括：丙硫菌唑10％～30％、乳化剂8％、聚合羧酸盐分散剂5％、黏度调节剂4％、消泡剂0.5％，余量为油；所述黏度调节剂为有机膨润土和气象白炭黑组成的混合物。本发明提供的丙硫菌唑可分散油悬浮剂性能稳定，相对于乳油剂型，本发明的丙硫菌唑可分散油悬浮剂减少了有机溶剂的使用，更环保、安全，贮运和使用安全，且对环境友好，符合当今农药剂型的发展方向，相对于水悬浮剂剂型，本发明的丙硫菌唑可分散油悬浮剂产品悬浮性能更稳定，有效期长，不会出现水悬产品严重沉淀的现象。
实验结果证明，该悬浮剂不仅悬浮稳定性高，满足不同水质地区、高海拔地区、低温地区、赤道附近高温地区的需要，又减少了有机溶剂对环境的影响。
为了进一步说明本发明，下面结合实施例对本发明提供的丙硫菌唑可分散油悬浮剂进行详细描述。
实施例1
丙硫菌唑10kg、三篦酸甘油脂聚氧乙烯醚8kg、聚丙烯酸钠5kg、有机膨润土0.5kg、气象白炭黑1.5kg、有机硅0.5kg，10kg改性大豆油，54.5kg油酸甲酯，10kg矿物油。
制备方法：
1)向混合釜内加入丙硫菌唑原药、三篦酸甘油脂聚氧乙烯醚、聚丙烯酸钠、有机硅、有机膨润土、气象白炭黑、改性大豆油、油酸甲酯、矿物油，在高剪切搅拌下，使物料充分混合均匀，将混合物料打入砂磨机中研磨，砂磨1～2h，得到丙硫菌唑可分散油悬浮剂。
实施例2
丙硫菌唑16kg、二苄基联苯基聚氧乙烯醚8kg、聚丙烯酸钠5kg、有机膨润土0.6kg、气象白炭黑1.8kg、有机硅0.5kg，11kg改性大豆油、46.1kg油酸甲酯和11kg矿物油。
制备方法：
1)向混合釜内加入丙硫菌唑原药、二苄基联苯基聚氧乙烯醚、聚丙烯酸钠、有机硅、有机膨润土、气象白炭黑和改性大豆油、油酸甲酯、矿物油，在高剪切搅拌下，使物料充分混合均匀，将混合物料打入砂磨机中研磨，砂磨1～2h，得到丙硫菌唑可分散油悬浮剂。
实施例3
丙硫菌唑20kg、苯乙烯基苯基聚氧乙烯醚8kg、聚丙烯酸钠5kg、有机膨润土0.5kg、气象白炭黑1.5kg、有机硅0.5kg，10kg改性大豆油、44.5kg油酸甲酯、10kg矿物油。
制备方法：
1)向混合釜内加入丙硫菌唑原药、苯乙烯基苯基聚氧乙烯醚、聚丙烯酸钠、有机硅、有机膨润土、气象白炭黑和改性大豆油、油酸甲酯、矿物油，在高剪切搅拌下，使物料充分混合均匀，将混合物料打入砂磨机中研磨，砂磨1～2h，得到丙硫菌唑可分散油悬浮剂。
实施例4
丙硫菌唑30kg、烷基酚甲醛树脂聚氧乙烯醚8kg、聚丙烯酸钠5kg、有机膨润土0.4kg、气象白炭黑1.2kg、有机硅0.5kg，10kg改性大豆油、34.9kg油酸甲酯和10kg矿物油。
制备方法：
1)向混合釜内加入丙硫菌唑原药、烷基酚甲醛树脂聚氧乙烯醚、聚丙烯酸钠、有机硅、有机膨润土、气象白炭黑和改性大豆油、油酸甲酯、矿物油，在高剪切搅拌下，使物料充分混合均匀，将混合物料打入砂磨机中研磨，砂磨1～2h，得到丙硫菌唑可分散油悬浮剂。
比较例1
按照实施例4的制备方法，配比如下：
丙硫菌唑30kg、烷基酚甲醛树脂聚氧乙烯醚8kg、NNO 5kg、有机膨润土0.4kg、气象白炭黑1.2kg、有机硅0.5kg，10kg改性大豆油、34.9kg油酸甲酯和10kg矿物油，制备丙硫菌唑可分散油悬浮剂。
比较例2
按照实施例4的制备方法，配比如下：
丙硫菌唑30kg、烷基酚甲醛树脂聚氧乙烯醚8kg、聚丙烯酸钠5kg、气象白炭黑1.6kg、有机硅0.5kg，10kg改性大豆油、34.9kg油酸甲酯和10kg矿物油，制备丙硫菌唑可分散油悬浮剂。
比较例3
按照实施例4的制备方法，配比如下：
丙硫菌唑30kg、烷基酚甲醛树脂聚氧乙烯醚8kg、聚丙烯酸钠0.5kg、有机膨润土1.6kg、有机硅0.5kg，10kg改性大豆油、34.9kg油酸甲酯和10kg矿物油，制备丙硫菌唑可分散油悬浮剂。
比较例4
按照实施例4的制备方法，配比如下：
丙硫菌唑30kg、烷基酚甲醛树脂聚氧乙烯醚8kg、聚丙烯酸钠5kg、有机膨润土0.4kg、气象白炭黑1.2kg、有机硅1kg，20kg改性大豆油、34.9kg油酸甲酯，制备丙硫菌唑可分散油悬浮剂。
实施例5
将实施例1～4、比较例1～4制备得到的丙硫菌唑可分散油悬浮剂进行性能指标检测，结果如表1：
表1 实施例1～4、比较例1～4丙硫菌唑可分散油悬浮剂性能检测结果
从表1可以看出，本发明制备的丙硫菌唑可分散油悬浮剂润湿性能优良，悬浮率较高，且贮存稳定性好，并且在-4℃和54℃下都具有很强的稳定性，满足低温、高温地区的需要。
由上述实施例及比较例可知，本发明提供的丙硫菌唑可分散油悬浮剂具有较高的悬浮稳定性。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (8)
- 一种丙硫菌唑可分散油悬浮剂，其特征在于，按照重量百分数计算，包括：丙硫菌唑10％～40％、乳化剂2％～10％、聚合羧酸盐分散剂2％～8％、黏度调节剂0.5％～6％、消泡剂0.1％～1％，余量为油；所述黏度调节剂为有机膨润土和气象白炭黑组成的混合物。
- 根据权利要求1所述的丙硫菌唑可分散油悬浮剂，其特征在于，所述有机膨润土和气象白炭黑的质量比为(1～3):(3～1)。
- 根据权利要求1所述的丙硫菌唑可分散油悬浮剂，其特征在于，所述乳化剂为三篦酸甘油脂聚氧乙烯醚、二苄基联苯基聚氧乙烯醚、苯乙烯基苯基聚氧乙烯醚、烷基酚甲醛树脂聚氧乙烯醚中的任意一种或多种。
- 根据权利要求1所述的丙硫菌唑可分散油悬浮剂，其特征在于，所述消泡剂为有机硅。
- 根据权利要求1所述的丙硫菌唑可分散油悬浮剂，其特征在于，所述油为改性大豆油、油酸甲酯、矿物油的混合物。
- 根据权利要求5所述的丙硫菌唑可分散油悬浮剂，其特征在于，所述改性大豆油、油酸甲酯和矿物油的质量比为(1～3):(1～6):(1～2)。
- 权利要求1～6任一项所述的丙硫菌唑可分散油悬浮剂的制备方法，包括以下步骤：将丙硫菌唑、乳化剂、聚合羧酸盐分散剂、黏度调节剂、消泡剂，油混合均匀，然后研磨，得到丙硫菌唑可分散油悬浮剂。
- 根据权利要求7所述的制备方法，其特征在于，所述研磨的时间为1～2h。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811598012.3 | 2018-12-26 | ||
| CN201811598012.3A CN109479885B (zh) | 2018-12-26 | 2018-12-26 | 丙硫菌唑可分散油悬浮剂 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020134105A1 true WO2020134105A1 (zh) | 2020-07-02 |
Family
ID=65712096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2019/100177 WO2020134105A1 (zh) | 2018-12-26 | 2019-08-12 | 丙硫菌唑可分散油悬浮剂 |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109479885B (zh) |
| WO (1) | WO2020134105A1 (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109479885B (zh) * | 2018-12-26 | 2020-11-13 | 安徽久易农业股份有限公司 | 丙硫菌唑可分散油悬浮剂 |
| CN110074119A (zh) * | 2019-05-10 | 2019-08-02 | 上海师范大学 | 戊唑醇可分散水悬浮剂及其制备方法 |
| CN110050793A (zh) * | 2019-05-22 | 2019-07-26 | 安徽久易农业股份有限公司 | 丙硫菌唑干悬浮剂、其制备方法及应用 |
| CN114176092A (zh) * | 2021-12-28 | 2022-03-15 | 利民化学有限责任公司 | 一种含有代森锰锌和丙硫菌唑的纳米油悬浮剂及其制备方法 |
| CN114403140A (zh) * | 2022-01-20 | 2022-04-29 | 上海启赟新材料有限公司 | 一种增稠稳定剂及其制备农药油悬浮剂的方法 |
| CN115226718A (zh) * | 2022-05-13 | 2022-10-25 | 安徽久易农业股份有限公司 | 一种含有枯草芽孢杆菌与丙硫菌唑的杀菌组合物及其制备方法和应用 |
| CN115403535B (zh) * | 2022-08-17 | 2024-02-02 | 吉林乐斯药业有限公司 | 一种去除丙硫菌唑中有机溶剂的提纯方法 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104255740A (zh) * | 2014-09-26 | 2015-01-07 | 陕西上格之路生物科学有限公司 | 一种含有草酸二丙酮胺铜和三唑类杀菌剂的杀菌组合物 |
| CN104522037A (zh) * | 2014-12-22 | 2015-04-22 | 中国中化股份有限公司 | 一种杀菌杀虫组合物及其应用 |
| CN106259369A (zh) * | 2016-08-03 | 2017-01-04 | 广东中迅农科股份有限公司 | 含有乙氧氟草醚和丙炔噁草酮的油悬浮剂及其制备方法 |
| CN106857532A (zh) * | 2017-04-28 | 2017-06-20 | 陕西上格之路生物科学有限公司 | 含啶酰菌胺的杀菌组合物在防治腐烂病上的应用 |
| CN106879600A (zh) * | 2017-04-11 | 2017-06-23 | 南京南农农药科技发展有限公司 | 一种杀菌组合物及其制备方法及用途 |
| CN107306967A (zh) * | 2017-07-10 | 2017-11-03 | 安徽丰乐农化有限责任公司 | 一种含有丙硫菌唑与氨基寡糖素的杀菌组合物 |
| CN109479885A (zh) * | 2018-12-26 | 2019-03-19 | 安徽久易农业股份有限公司 | 丙硫菌唑可分散油悬浮剂 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106489964A (zh) * | 2016-10-21 | 2017-03-15 | 青岛瀚生生物科技股份有限公司 | 含矿物油的螺虫乙酯可分散油悬浮剂及其制备方法、应用 |
| CN106719709A (zh) * | 2016-12-02 | 2017-05-31 | 佛山市普尔玛农化有限公司 | 一种含二氯噁菌唑和氟啶胺的农药组合物 |
| CN107372585A (zh) * | 2017-08-18 | 2017-11-24 | 佛山市盈辉作物科学有限公司 | 一种除草剂组合物 |
-
2018
- 2018-12-26 CN CN201811598012.3A patent/CN109479885B/zh active Active
-
2019
- 2019-08-12 WO PCT/CN2019/100177 patent/WO2020134105A1/zh active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104255740A (zh) * | 2014-09-26 | 2015-01-07 | 陕西上格之路生物科学有限公司 | 一种含有草酸二丙酮胺铜和三唑类杀菌剂的杀菌组合物 |
| CN104522037A (zh) * | 2014-12-22 | 2015-04-22 | 中国中化股份有限公司 | 一种杀菌杀虫组合物及其应用 |
| CN106259369A (zh) * | 2016-08-03 | 2017-01-04 | 广东中迅农科股份有限公司 | 含有乙氧氟草醚和丙炔噁草酮的油悬浮剂及其制备方法 |
| CN106879600A (zh) * | 2017-04-11 | 2017-06-23 | 南京南农农药科技发展有限公司 | 一种杀菌组合物及其制备方法及用途 |
| CN106857532A (zh) * | 2017-04-28 | 2017-06-20 | 陕西上格之路生物科学有限公司 | 含啶酰菌胺的杀菌组合物在防治腐烂病上的应用 |
| CN107306967A (zh) * | 2017-07-10 | 2017-11-03 | 安徽丰乐农化有限责任公司 | 一种含有丙硫菌唑与氨基寡糖素的杀菌组合物 |
| CN109479885A (zh) * | 2018-12-26 | 2019-03-19 | 安徽久易农业股份有限公司 | 丙硫菌唑可分散油悬浮剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109479885B (zh) | 2020-11-13 |
| CN109479885A (zh) | 2019-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020134105A1 (zh) | 丙硫菌唑可分散油悬浮剂 | |
| CN102805090A (zh) | 一种吡唑醚菌酯水悬浮剂及其制备方法 | |
| TWI772416B (zh) | 一種吡唑醚菌酯水分散固體組合物及其製備方法 | |
| CN107535489A (zh) | 一种低容量或超低容量喷雾施药的专用增效剂及其制备方法与应用 | |
| CN108308179B (zh) | 农药增效助剂及含有该助剂的除草组合物 | |
| CN101978829A (zh) | 一种含联苯肼酯与螺螨酯的农药组合物 | |
| CN103250720A (zh) | 一种含氟啶脲和zj4042农业杀虫组合物 | |
| CN109169646B (zh) | 一种呋虫胺可分散油悬浮剂及其制备方法 | |
| CN112314597A (zh) | 一种水悬浮剂的制备方法 | |
| CN111264529A (zh) | 一种含唑螨酯的组合物 | |
| RU2163759C2 (ru) | Гербицидный состав | |
| CN115886019A (zh) | 一种含吡嘧磺隆与二甲四氯异辛酯的可分散油悬浮剂及其制备方法和应用 | |
| CN103583520A (zh) | 一种硝磺草酮可分散油悬浮剂及其制备方法 | |
| CN107517959A (zh) | 一种含甲基二磺隆和炔草酯的可分散油悬浮剂及其制备方法 | |
| CN100350840C (zh) | 杀菌组合物 | |
| CN107568244B (zh) | 四氯虫酰胺与敌百虫的杀虫组合物及其用途 | |
| CN102334510A (zh) | 一种吡蚜酮与毒死蜱复配悬乳剂 | |
| CN101601402B (zh) | 含有喹禾灵的除草组合物 | |
| JP2004010492A (ja) | 効力を増強された農園芸用混合殺菌組成物 | |
| CN104642302B (zh) | 苏云金芽孢杆菌可分散油悬乳剂及其制备方法 | |
| CN101194615B (zh) | 鱼藤酮与抑食肼混配农药制剂 | |
| CN106719642A (zh) | 风车子抑素a4悬浮剂、制备方法及其应用 | |
| CN103651509A (zh) | 防治水稻刺吸口器类昆虫的组合物 | |
| CN110463708A (zh) | 一种稻根叶甲杀虫剂 | |
| CN114946870B (zh) | 一种五氟磺草胺和砜吡草唑可分散油悬浮剂及其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19905819 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 19905819 Country of ref document: EP Kind code of ref document: A1 |