CN117546840A - 1-methylcyclopropene oil suspension agent and preparation method thereof - Google Patents
1-methylcyclopropene oil suspension agent and preparation method thereof Download PDFInfo
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- CN117546840A CN117546840A CN202311495433.4A CN202311495433A CN117546840A CN 117546840 A CN117546840 A CN 117546840A CN 202311495433 A CN202311495433 A CN 202311495433A CN 117546840 A CN117546840 A CN 117546840A
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- methylcyclopropene
- oil
- cyclodextrin
- agent
- oil suspension
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- SHDPRTQPPWIEJG-UHFFFAOYSA-N 1-methylcyclopropene Chemical compound CC1=CC1 SHDPRTQPPWIEJG-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000005969 1-Methyl-cyclopropene Substances 0.000 title claims abstract description 152
- 239000012053 oil suspension Substances 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 55
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003921 oil Substances 0.000 claims abstract description 41
- 239000000375 suspending agent Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 20
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 claims abstract description 17
- 239000002562 thickening agent Substances 0.000 claims abstract description 17
- 239000002609 medium Substances 0.000 claims abstract description 14
- 239000012736 aqueous medium Substances 0.000 claims abstract description 10
- 235000019198 oils Nutrition 0.000 claims description 37
- 238000000227 grinding Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 13
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 11
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 11
- 235000012055 fruits and vegetables Nutrition 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- 241000196324 Embryophyta Species 0.000 claims description 8
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 6
- 229940073769 methyl oleate Drugs 0.000 claims description 6
- 235000005687 corn oil Nutrition 0.000 claims description 5
- 239000002285 corn oil Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 4
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000001116 FEMA 4028 Substances 0.000 claims description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 3
- 229960004853 betadex Drugs 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 3
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 3
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 230000009758 senescence Effects 0.000 claims description 2
- 230000002028 premature Effects 0.000 claims 1
- 230000005070 ripening Effects 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000575 pesticide Substances 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 7
- 235000013399 edible fruits Nutrition 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 235000013311 vegetables Nutrition 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OOXWYYGXTJLWHA-UHFFFAOYSA-N cyclopropene Chemical compound C1C=C1 OOXWYYGXTJLWHA-UHFFFAOYSA-N 0.000 description 4
- 239000007938 effervescent tablet Substances 0.000 description 4
- 238000005338 heat storage Methods 0.000 description 4
- 108091054761 ethylene receptor family Proteins 0.000 description 3
- FAPGNCCCFGCZKP-UHFFFAOYSA-N 3-methylcyclopropene Chemical compound CC1C=C1 FAPGNCCCFGCZKP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001943 cyclopropenes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 240000003152 Rhus chinensis Species 0.000 description 1
- 235000014220 Rhus chinensis Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 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 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005089 fruit drop Effects 0.000 description 1
- 230000004345 fruit ripening Effects 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 108020003175 receptors Proteins 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
-
- 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
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P21/00—Plant growth regulators
Abstract
The invention belongs to the technical field of pesticide preparations, and particularly relates to a 1-methylcyclopropene oil suspension agent and a preparation method thereof. According to the invention, the cyclodextrin inclusion compound of the 1-methylcyclopropene is dispersed into a non-aqueous medium, so that the quick release caused by the contact of the cyclodextrin inclusion compound of the 1-methylcyclopropene with water is avoided, and the stability of the 1-methylcyclopropene oil suspending agent is improved; meanwhile, the phosphatidylcholine, the emulsifying agent, the thickening agent and other auxiliary agents are matched for use, so that the problem of high viscosity caused by the dispersion of cyclodextrin in an oil medium is solved, the proper viscosity of the 1-methylcyclopropene oil suspending agent is ensured, the use and the storage are facilitated, the environment is protected, and the novel high-viscosity oil suspending agent can be used in an open space and a closed space at the same time.
Description
Technical Field
The invention belongs to the technical field of pesticide preparations, and particularly relates to a 1-methylcyclopropene oil suspension agent and a preparation method thereof.
Background
Ethylene is a common compound, mainly derived from ripe fruits. Whether exogenous ethylene or endogenous ethylene can induce a series of physiological and biochemical reactions in the growth and development process of plants, such as promotion of germination, root spreading, flower bloom and fruit ripening, etc., and is an important plant growth regulator. However, it is a major problem for fruits, vegetables, etc. that it takes time to transport and store, and how to maintain freshness of fruits and vegetables during transportation and storage. It is counted that the losses of horticultural products such as flowers, vegetables and fruits around the world due to improper storage are about 30% of the total amount, and that l5-25% of them are all caused by aging due to ethylene. Effectively controlling the generation and the action of ethylene is helpful for delaying the senescence of fruits and vegetables and prolonging the postharvest life of the fruits and the vegetables. One important aspect is the use of ethylene receptor inhibitors to modulate ethylene physiology. Ethylene receptor inhibitors compete for ethylene receptors in plants, bind to the receptors reversibly or irreversibly, hinder the normal binding of ethylene, and thus inhibit a series of physiological and biochemical processes induced by it. Cyclopropene compounds such as Cyclopropene (CP), 1-methylcyclopropene (1-MCP), 3-methylcyclopropene (3-MCP), 3-dimethylcyclopropene (3, 3-DMCP) and the like can competitively antagonize ethylene effect, block ethylene signal transmission and inhibit ethylene induction and physiological effect exertion, and the discovery of the compounds also provides a new tool for controlling post-harvest aging of fruits and vegetables. Among these cyclopropene compounds, 1-methylcyclopropene is particularly effective. The compound is in a gaseous state at 10 ℃, has relatively stable property, strong activity, no peculiar smell, extremely low concentration required by treatment, and no toxic effect on human and livestock in a concentration range capable of preventing ethylene response and guaranteeing fruit and vegetable tissues. Therefore, the method has important theoretical significance and potential commercial application value in prolonging the postharvest life of fruits and vegetables and researching ethylene metabolism.
At present, the 1-methylcyclopropene is generally used as effervescent tablets after being coated with cyclodextrin, but the effervescent tablets are required to be used in a closed space, so that the application range of the effervescent tablets is greatly limited. The 1-methylcyclopropene is prepared into an oil suspension agent, can be sprayed for use, expands the application range, and can be used in a closed or open space. But also can be sprayed on orchards and vegetable fields to prevent fruit drop and delay the aging of vegetables, fruits and gardening products, and has great significance for the application and popularization of 1-methylcyclopropene. Chinese patent CN108703139 discloses a 1-methylcyclopropene oil suspension comprising an oil suspension diluted with oil and a dispersible oil suspension diluted with water, wherein the 1-methylcyclopropene is encapsulated with a suitable material and then prepared into a formulation. However, the microencapsulation of 1-methylcyclopropene is difficult and costly, and the microcapsule material cannot be completely degraded, so that there is a potential problem of incomplete release and a potential environmental risk. Chinese patent CN101356917a discloses the solution of obtaining an oil formulation after grinding cyclopropene species in an oil medium, which can be applied to plants, preventing them from maturing early. However, cyclodextrin is a polysaccharide substance, and after grinding in a medium, the cyclodextrin often has very high viscosity, and a product with high viscosity is not convenient for normal temperature storage and is also inconvenient to use. Therefore, compared with 1-methylcyclopropene effervescent tablets, the existing 1-methylcyclopropene oil suspending agent can be used in an open space, but still has the problems of poor stability and inconvenient storage, and has high destructive influence on the environment.
Disclosure of Invention
The invention aims to provide a 1-methylcyclopropene oil suspension agent and a preparation method thereof, wherein the 1-methylcyclopropene oil suspension agent has good stability, is easy to store and is environment-friendly.
The invention provides a 1-methylcyclopropene oil suspending agent, which is prepared from the following raw materials in percentage by mass: 0.1-2% of 1-methylcyclopropene, 5-15% of an emulsifier, 0.1-5% of phosphatidylcholine, 0.5-2% of a thickener and the balance of a non-aqueous medium;
the 1-methylcyclopropene is used in the form of a cyclodextrin inclusion complex of 1-methylcyclopropene.
Preferably, the cyclodextrin inclusion compound of the 1-methylcyclopropene comprises cyclodextrin and 1-methylcyclopropene which is included in an inner cavity of the cyclodextrin, wherein the mass ratio of the cyclodextrin inclusion compound of the 1-methylcyclopropene to the 1-methylcyclopropene is 1-3:100.
preferably, the cyclodextrin comprises α -cyclodextrin, β -cyclodextrin or γ -cyclodextrin.
Preferably, the viscosity of the 1-methylcyclopropene oil suspension agent is 300-1000 mPas.
Preferably, the emulsifier comprises several of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, dioctyl sodium sulfosuccinate and dodecylbenzene sulfonate.
Preferably, the nonaqueous medium comprises one or more of soybean oil, corn oil and methyl oleate.
Preferably, the thickener comprises fumed silica and/or organic bentonite.
The invention also provides a preparation method of the 1-methylcyclopropene oil suspension agent, which comprises the following steps:
mixing cyclodextrin inclusion compound of 1-methylcyclopropene, an emulsifying agent, phosphatidylcholine, a thickening agent and a nonaqueous medium, and grinding the obtained mixed solution to 2-3 mu m to obtain a grinding mixture;
and (3) carrying out solid-liquid separation on the grinding mixture to obtain the 1-methylcyclopropene oil suspension agent.
Preferably, the temperature of the milling is below 40 ℃.
The invention also provides a method for delaying fruit and vegetable aging and/or preventing fruit and vegetable from maturing in advance, which comprises the following steps: the 1-methylcyclopropene oil suspending agent is contacted with plants for use in a spraying, smearing or dipping mode; the 1-methylcyclopropene oil suspending agent is the 1-methylcyclopropene oil suspending agent according to the technical scheme or the 1-methylcyclopropene oil suspending agent obtained by the preparation method according to the technical scheme.
The beneficial effects are that:
the invention provides a 1-methylcyclopropene oil suspending agent, which is prepared from the following raw materials in percentage by mass: 0.1% -2% of 1-methylcyclopropene, 5% -15% of an emulsifier, 0.1% -5% of phosphatidylcholine, 0.5% -2% of a thickener and the balance of a non-aqueous medium; the 1-methylcyclopropene is used in the form of a cyclodextrin inclusion complex of 1-methylcyclopropene. According to the invention, the cyclodextrin inclusion compound of the 1-methylcyclopropene is dispersed into a non-aqueous medium, so that the quick release caused by the contact of the cyclodextrin inclusion compound of the 1-methylcyclopropene with water is avoided, and the stability of the 1-methylcyclopropene oil suspending agent is improved; meanwhile, the phosphatidylcholine, the emulsifying agent, the thickening agent and other auxiliary agents are matched for use, so that the problem of high viscosity caused by the dispersion of cyclodextrin in an oil medium is solved, the proper viscosity of the 1-methylcyclopropene oil suspending agent is ensured, the use and the storage are facilitated, the environment is protected, and the use in an open space and a closed space can be met.
Detailed Description
The invention provides a 1-methylcyclopropene oil suspending agent, which is prepared from the following raw materials in percentage by mass: 0.1-2% of 1-methylcyclopropene, 5-15% of an emulsifier, 0.1-5% of phosphatidylcholine, 0.5-2% of a thickener and the balance of a non-aqueous medium;
the 1-methylcyclopropene is used in the form of a cyclodextrin inclusion complex of 1-methylcyclopropene.
The 1-methylcyclopropene oil suspension agent of the present invention comprises 0.1% -2% by mass of 1-methylcyclopropene, more preferably 0.5% -1.5% by mass, and still more preferably 1% -1.5% by mass. The 1-methylcyclopropene is used in the form of cyclodextrin inclusion complex of the 1-methylcyclopropene; the cyclodextrin inclusion compound of the 1-methylcyclopropene preferably comprises cyclodextrin and 1-methylcyclopropene which is included in the inner cavity of the cyclodextrin, and the mass ratio of the cyclodextrin inclusion compound of the 1-methylcyclopropene to the 1-methylcyclopropene is preferably 1-3:100, more preferably 3:100. the cyclodextrin inclusion compound of the 1-methylcyclopropene is preferably obtained by purchasing, and the purchasing source is not particularly limited, so that the mass ratio of the 1-methylcyclopropene to the cyclodextrin in the cyclodextrin inclusion compound of the 1-methylcyclopropene is satisfied. The cyclodextrin of the present invention preferably comprises alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin, more preferably alpha-cyclodextrin. The cyclodextrin is used for inclusion of the 1-methylcyclopropene, so that the stability of the 1-methylcyclopropene can be enhanced, and the release rate of the 1-methylcyclopropene can be reduced.
The 1-methylcyclopropene oil suspension agent comprises 5% -15% of an emulsifying agent, preferably 7% -11% of the emulsifying agent and further preferably 8% -10% of the emulsifying agent in percentage by mass. The emulsifier preferably comprises several of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, dioctyl sodium sulfosuccinate and dodecylbenzene sulfonate; several emulsifiers are used in combination to facilitate the stability of the system.
The 1-methylcyclopropene oil suspension agent comprises 0.1% -5% of phosphatidylcholine, preferably 0.5% -3.0%, and more preferably 1% -2% of phosphatidylcholine. The phosphatidylcholine is used as a viscosity regulator, can help to reduce the viscosity of the preparation after cyclodextrin is dispersed, and ensures that the 1-methylcyclopropene oil suspending agent has higher stability and is easier to transport and store.
The 1-methylcyclopropene oil suspension agent comprises 0.5% -2% of a thickening agent, preferably 0.5% -1% of the thickening agent by mass percent. The thickener according to the invention preferably comprises fumed silica and/or an organobentonite, more preferably fumed silica or an organobentonite.
The 1-methylcyclopropene oil suspension agent of the present invention preferably further comprises a non-aqueous medium in addition to the cyclodextrin inclusion compound of 1-methylcyclopropene, the emulsifier, phosphatidylcholine and the thickener described above, in terms of mass percent. The nonaqueous medium of the present invention preferably includes one or more of soybean oil, corn oil and methyl oleate, more preferably soybean oil, corn oil or methyl oleate. The nonaqueous medium according to the invention is preferably used as a diluent. According to the invention, the nonaqueous medium is used for replacing water to dilute other components in the 1-methylcyclopropene oil suspension agent, so that the release rate of the 1-methylcyclopropene is reduced, and the quick release of the 1-methylcyclopropene after meeting water is avoided.
The viscosity of the 1-methylcyclopropene oil suspending agent is preferably 300-1000 mPas, more preferably 450-588 mPas, and the 1-methylcyclopropene oil suspending agent within the viscosity range is favorable for stabilizing the 1-methylcyclopropene oil suspending agent and is convenient to use and store.
The invention also provides a preparation method of the 1-methylcyclopropene oil suspension agent, which comprises the following steps:
mixing cyclodextrin inclusion compound of 1-methylcyclopropene, an emulsifying agent, phosphatidylcholine, a thickening agent and a nonaqueous medium, and grinding the obtained mixed solution to 2-3 mu m to obtain a grinding mixture;
and (3) carrying out solid-liquid separation on the grinding mixture to obtain the 1-methylcyclopropene oil suspension agent.
The invention mixes cyclodextrin inclusion compound of 1-methylcyclopropene, emulsifying agent, phosphatidylcholine, thickening agent and nonaqueous medium, and grinds the obtained mixed solution to 2-3 mu m to obtain grinding mixture. After the mixing, the obtained mixed solution is preferably stirred so as to uniformly mix the components. The mixed liquid is preferably ground by using a grinder, the type and parameters of which are not particularly limited, and the grinder and grinding parameters conventional in the art are adopted. The grinding temperature is preferably lower than 40 ℃ so as to ensure that the materials cannot change in state due to overhigh temperature in the grinding process. The 2-3 μm milling mixture of the present invention allows the components to be dispersed in the form of fine particles in a non-aqueous medium.
After the grinding mixture is obtained, the grinding mixture is subjected to solid-liquid separation, and the 1-methylcyclopropene oil suspending agent is obtained. The solid-liquid separation mode is preferably filtration, and the filtration parameters are not particularly limited, and the conventional parameters in the field can be adopted.
According to the invention, the cyclodextrin inclusion compound of the 1-methylcyclopropene is dispersed into a non-aqueous medium, so that the quick release caused by the contact of the cyclodextrin inclusion compound of the 1-methylcyclopropene with water is avoided, and the stability of the 1-methylcyclopropene oil suspending agent is improved; meanwhile, the phosphatidylcholine, the emulsifying agent, the thickening agent and other auxiliary agents are matched for use, so that the problem of high viscosity caused by the dispersion of cyclodextrin in an oil medium is solved, the proper viscosity of the 1-methylcyclopropene oil suspending agent is ensured, the use and the storage are facilitated, the environment is protected, and the novel high-viscosity oil suspending agent can be used in an open space and a closed space at the same time.
The 1-methylcyclopropene oil suspending agent disclosed by the invention can be contacted with plants to play a role in a spraying, smearing or dipping mode, and the use modes are various, so that the method for contacting the 1-methylcyclopropene oil suspending agent with the plants in a spraying, smearing or dipping mode to delay the aging of fruits and vegetables and/or prevent the fruits and vegetables from maturing in advance also belongs to the protection scope of the invention, and especially the service life of the fruits and vegetables after being picked is prolonged. The dosage of the 1-methylcyclopropene oil suspension agent is not particularly limited, and the suspension agent can be adjusted conventionally according to requirements. The plants of the invention preferably comprise fruits and/or vegetables.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
0.1% of 1-methylcyclopropene oil suspending agent, which comprises the following components in percentage by mass:
weighing materials according to the above formula, wherein 1-methylcyclopropene is used as 1-methylcyclopropene coated with cyclodextrin (the mass ratio of 1-methylcyclopropene coated with alpha-cyclodextrin to 1-methylcyclopropene is 100:3), mixing, and grinding to median particle diameter D with vertical sand mill at 35deg.C 50 After filtration, 0.1% 1-methylcyclopropene oil suspension was obtained =2.52 μm.
Example 2
0.5% of 1-methylcyclopropene oil suspending agent, which comprises the following components in percentage by mass:
weighing materials according to the above formula, wherein 1-methylcyclopropene is used as 1-methylcyclopropene coated with cyclodextrin (the mass ratio of 1-methylcyclopropene coated with alpha-cyclodextrin to 1-methylcyclopropene is 100:3), mixing, and grinding to median particle diameter D with vertical sand mill at 30deg.C 50 =2.30 μm, and 0.5% 1-methyl is obtained after filtrationA cyclopropene oil suspending agent.
Example 3
1% of 1-methylcyclopropene oil suspending agent, which comprises the following components in percentage by mass:
weighing materials according to the above formula, wherein 1-methylcyclopropene is used as 1-methylcyclopropene coated with cyclodextrin (the mass ratio of 1-methylcyclopropene coated with alpha-cyclodextrin to 1-methylcyclopropene is 100:3), mixing, and grinding to median particle diameter D with a vertical sand mill at 30deg.C 50 After filtration, 1% 1-methylcyclopropene oil suspension was obtained =2.30 μm.
Example 4
1.5% of 1-methylcyclopropene oil suspending agent, which comprises the following components in percentage by mass:
weighing materials according to the above formula, wherein 1-methylcyclopropene is used as 1-methylcyclopropene coated with cyclodextrin (the mass ratio of 1-methylcyclopropene coated with alpha-cyclodextrin to 1-methylcyclopropene is 100:3), mixing, and grinding to median particle diameter D with vertical sand mill at 35deg.C 50 After filtration, 1.5% 1-methylcyclopropene oil suspension was obtained =2.09 μm.
Example 5
The 2% 1-methylcyclopropene oil suspending agent comprises the following components in percentage by mass:
weighing materials according to the above formula, wherein 1-methylcyclopropene is used as 1-methylcyclopropene coated with cyclodextrin (the mass ratio of 1-methylcyclopropene coated with alpha-cyclodextrin to 1-methylcyclopropene is 100:3), mixing, and grinding to median particle diameter D with a vertical sand mill at 30deg.C 50 After filtration, 1.5% 1-methylcyclopropene oil suspension was obtained =2.31 μm.
In the above examples, 1-methylcyclopropene was entrapped with alpha-cyclodextrin as an inclusion agent, and was obtained from 1-methylcyclopropene cyclodextrin inclusion compounds having a 1-methylcyclopropene content of 3% and available from Shandong Zhiyuan Biotechnology Co.Ltd. The components such as the emulsifier can be purchased from commercial sources, such as pesticide emulsion 1602 from Nanjing Ethernet; dioctyl sodium sulfosuccinate was purchased from Hebei Yancheng chemical Co., ltd; calcium dodecylbenzenesulfonate was purchased from bell mountain chemical limited; aerosil 974, SK 04 were purchased from sumac midrange mineral materials limited. Methyl oleate, soybean oil, corn oil are all commercially available.
Comparative example 1
1% of 1-methylcyclopropene oil suspending agent, which comprises the following components in percentage by mass:
weighing materials according to the above formula, wherein 1-methylcyclopropene is used as 1-methylcyclopropene inclusion compound of cyclodextrin inclusion (the mass ratio of 1-methylcyclopropene to 1-methylcyclopropene of alpha-cyclodextrin inclusion is 100:3), mixing uniformly, and grinding to median particle diameter D with a vertical sand mill at 30deg.C 50 After filtration, 1% 1-methylcyclopropene oil suspension was obtained, the samples were creamed at room temperature and heat storage, the phosphatidylcholine in examples 2-5 was removed, the missing phosphatidylcholine was complemented with the corresponding nonaqueous medium in each example, samples were prepared according to the preparation method of example 1, the samples were creamed at room temperature and heat storage,the heat storage test is measured by referring to the method of GB/T19136-2003 pesticide low temperature stability.
Example 6
Quality technical index of 1-methylcyclopropene oil suspension agent
At present, no technical standard of a 1-methylcyclopropene suspending agent exists, so that detection is carried out by referring to a general quality technical index of the suspending agent, a link of diluting the suspending agent by water in the standard of the suspending agent adopts methyl oleate to replace water, and the rest of testing steps are the same as those of the suspending agent (GB 18171-2000). The 1-methylcyclopropene oil suspension prepared in examples 1-5 did not exhibit creaming and caking after cold and hot storage tests.
The conditions for the viscosity test were: a Brookfield viscosity tester, rotor # 3, was used at 60rpm. Content testing was performed using gas chromatography, performed on a Agilent Technologies 6890N gas chromatograph. Experimental conditions: HP-PLOTQ column (USA, carrier A1203), column length 30m, inner diameter 0.53mm, film thickness 40 μm, flame Ionization Detector (FID), detector temperature 250 ℃, air flow 450mL/min, hydrogen flow 40mL/min, make-up gas flow 45mL/min, nitrogen as carrier gas, flow 5.0mL/min, column pressure head 3.98psi, injection port temperature 200 ℃, initial temperature 50 ℃, rising at a rate of 20 ℃/min, reaching final temperature 250 ℃. The heat storage stability of 1-methylcyclopropene oil suspensions is described in GB/T19136-2003 with reference to 2.3; cold storage stability is carried out by referring to the method of low temperature stability of GB/T19136-2003 pesticides. The results are shown in Table 1:
table 1 1-quality technical index of methylcyclopropene oil suspension
From the above embodiments it can be derived that: the 1-methylcyclopropene oil suspending agent disclosed by the invention is higher in stability and wider in application range.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. The 1-methylcyclopropene oil suspension agent is characterized by being prepared from the following raw materials in percentage by mass: 0.1-2% of 1-methylcyclopropene, 5-15% of an emulsifier, 0.1-5% of phosphatidylcholine, 0.5-2% of a thickener and the balance of a non-aqueous medium;
the 1-methylcyclopropene is used in the form of a cyclodextrin inclusion complex of 1-methylcyclopropene.
2. The 1-methylcyclopropene oil suspension of claim 1, wherein the cyclodextrin inclusion compound of 1-methylcyclopropene comprises cyclodextrin and 1-methylcyclopropene included in an inner cavity of the cyclodextrin, and a mass ratio of the cyclodextrin inclusion compound of 1-methylcyclopropene to 1-methylcyclopropene is 1-3:100.
3. the 1-methylcyclopropene oil suspension of claim 2, wherein the cyclodextrin comprises alpha cyclodextrin, beta cyclodextrin or gamma cyclodextrin.
4. A 1-methylcyclopropene oil suspension according to any of claims 1 to 3, characterized in that the viscosity of the 1-methylcyclopropene oil suspension is 300-1000 mPa-s.
5. The 1-methylcyclopropene oil suspension of claim 1, wherein the emulsifier comprises several of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, dioctyl sodium sulfosuccinate and dodecylbenzene sulfonate.
6. The 1-methylcyclopropene oil suspension of claim 1, wherein the non-aqueous medium comprises one or more of soybean oil, corn oil and methyl oleate.
7. The 1-methylcyclopropene oil suspension of claim 1, wherein the thickener comprises fumed silica and/or organobentonite.
8. The method for preparing the 1-methylcyclopropene oil suspension agent as claimed in any one of claims 1-7, comprising the steps of:
mixing cyclodextrin inclusion compound of 1-methylcyclopropene, an emulsifying agent, phosphatidylcholine, a thickening agent and a nonaqueous medium, and grinding the obtained mixed solution to 2-3 mu m to obtain a grinding mixture;
and (3) carrying out solid-liquid separation on the grinding mixture to obtain the 1-methylcyclopropene oil suspension agent.
9. The method of claim 8, wherein the milling is at a temperature of less than 40 ℃.
10. A method for delaying senescence and/or preventing premature ripening of fruits and vegetables, comprising: the 1-methylcyclopropene oil suspending agent is contacted with plants for use in a spraying, smearing or dipping mode; the 1-methylcyclopropene oil suspending agent is the 1-methylcyclopropene oil suspending agent according to any one of claims 1 to 7 or the 1-methylcyclopropene oil suspending agent obtained by the preparation method according to claim 8 or 9.
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