WO2021134157A1 - 一种含有磷酸铁螯合物的环保杀螺剂及其制备方法 - Google Patents

一种含有磷酸铁螯合物的环保杀螺剂及其制备方法 Download PDF

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Publication number
WO2021134157A1
WO2021134157A1 PCT/CN2019/129756 CN2019129756W WO2021134157A1 WO 2021134157 A1 WO2021134157 A1 WO 2021134157A1 CN 2019129756 W CN2019129756 W CN 2019129756W WO 2021134157 A1 WO2021134157 A1 WO 2021134157A1
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WIPO (PCT)
Prior art keywords
iron phosphate
environmentally friendly
molluscicide
containing iron
chelate
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PCT/CN2019/129756
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English (en)
French (fr)
Inventor
杨凯
叶素芬
Original Assignee
徐州益农化工有限公司
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Filing date
Publication date
Application filed by 徐州益农化工有限公司 filed Critical 徐州益农化工有限公司
Priority to EP19874758.6A priority Critical patent/EP3868208B1/en
Priority to PCT/CN2019/129756 priority patent/WO2021134157A1/zh
Priority to CN201980003494.XA priority patent/CN111132551B/zh
Publication of WO2021134157A1 publication Critical patent/WO2021134157A1/zh

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Classifications

    • 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
    • A01P9/00—Molluscicides
    • 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
    • A01N25/002—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 a foodstuff as carrier or diluent, i.e. baits
    • A01N25/008—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 a foodstuff as carrier or diluent, i.e. baits molluscicidal
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/26—Phosphorus; Compounds thereof

Definitions

  • This application relates to the field of mollusc prevention and control. More specifically, this application relates to an environmentally friendly molluscicide containing iron phosphate chelate and a preparation method thereof.
  • Molluscs that harm crops mainly include snails (commonly known as buffalo or dry snails), slugs, snails (commonly known as snails), snails and snails.
  • the occurrence of mollusks is large.
  • the snails are hermaphroditic and can lay up to 300 eggs at a time, and can lay 300-2000 eggs in a year; Fushou snails are dioecious, and each female snail can lay 200-500 eggs at a time, and each egg can be used for 50 days. It can be matured and reproduced and iterated in the field.
  • Snails and snails are greedy, biting on the young shoots, young leaves and tender stems of crops, and can cause a large number of wounds on the roots, stems and leaves, which is conducive to the invasion of fungi, bacteria and viruses and other pathogenic bacteria, which increases the damage of crops.
  • Mollusks are widely distributed in humid and warm areas of the world, and seriously endanger crops such as gardening, grains, fruits, vegetables, cotton and tobacco. The more serious one is Oncomelania snails, the only intermediate host of schistosomiasis and an indispensable link in the transmission of schistosomiasis.
  • Snail amine, snail amine ethanol ammonium salt and acetaldehyde are the main varieties of snailicides at present.
  • spironilamine and ethanolammonium salts are highly toxic to fish, frogs, shellfish and other aquatic organisms, and pollute water bodies easily causing phytotoxicity. Because of their strong toxicity and high residues, they are also prohibited from being used in vegetables, fruits and horticulture. , It is mainly used to kill Oncomelania snails and control snails on rice, so the application range is narrow.
  • the dry powder and concentrated solution have a stimulating effect on the human mucous membranes, and can cause symptoms such as tearing, eye irritation, nasal congestion, runny nose, dry throat, and hoarseness.
  • acetaldehyde is low-toxic to aquatic organisms, it has strong acute toxicity and is harmful to birds and other wild animals. It is hardly soluble in water and has poor degradability in soil. It has been reported in the United Kingdom that tetramerization in groundwater has been reported. The residual acetaldehyde exceeds the standard.
  • molluscicide that is safe and low-toxic to humans, aquatic organisms and wild animals, has good solubility in the soil and is easily absorbed by plants, so that it will not accumulate in the soil in large quantities and cause soil ecology. problem.
  • the first aspect of this application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • Its raw materials include iron phosphate chelate, filler and water;
  • the agent includes at least one of corn starch, wheat starch, soybean starch, tapioca starch and distarch phosphate, preferably distarch phosphate.
  • the preparation raw material of the environmentally friendly molluscicide containing iron phosphate chelate further includes a binder; the binder includes natural wax, chemically modified wax, starch, At least one of alginate, agar, lignosulfonate, gum arabic and modified chitosan is preferably modified chitosan.
  • the modified chitosan is citric acid modified chitosan.
  • the raw material for the preparation of the environmentally friendly molluscicide containing iron phosphate chelate also includes a lubricant;
  • the lubricant includes magnesium stearate, sodium lauryl sulfate, vegetable oil and At least one of the hydroxylated vegetable oils is preferably a hydroxylated vegetable oil.
  • the iron phosphate chelate is formed by chelating iron phosphate and a chelating agent; the weight ratio of the iron phosphate and the chelating agent is 1:(0.025-40).
  • the weight ratio of the iron phosphate and the chelating agent is 1:(0.2-5), preferably 1:(0.8-1.2).
  • the chelating agent includes glutamate diacetic acid and its corresponding salt, iminodisuccinic acid and its corresponding salt, dicarboxymethylalanine and its corresponding salt, At least one of ethylenediamine disuccinic acid and its corresponding salt, and methylglycine diacetic acid and its corresponding salt.
  • the weight ratio of the citric acid-modified chitosan and the hydroxylated vegetable oil is (0.2-5):1, preferably (0.2-1.5):1.
  • the second aspect of the present application provides a method for preparing an environmentally friendly molluscicide containing iron phosphate chelate, which includes: putting the raw materials of the environmentally friendly molluscicide containing iron phosphate chelate into a pelletizing plate Granules are dried to prepare an environmentally friendly molluscicide containing iron phosphate chelate.
  • the third aspect of this application provides an environmentally friendly molluscicide containing iron phosphate chelate for use in terrestrial and aquatic environments.
  • the molluscicide provided in this application is harmless to humans and aquatic organisms, and harmless to pets and wild animals. At the same time, it can improve the solubility of iron phosphate in the soil, so that it can be absorbed by crops as a phosphate fertilizer, which not only solves the problem of iron phosphate in the soil. The problem of degradation residues in the molluscs also gives nutrients to the crops, ensuring the harmlessness and safety of the molluscicide to the ecological environment.
  • the first aspect of this application provides an environmentally friendly molluscicide containing iron phosphate chelate, and its preparation raw materials include iron phosphate chelate, filler and water.
  • the raw material for preparing the environmentally friendly molluscicide containing iron phosphate chelate further includes a binder.
  • the raw material for preparing the environmentally friendly molluscicide containing iron phosphate chelate further includes a lubricant.
  • the raw materials for preparing the environmentally friendly molluscicide containing iron phosphate chelate further include pigments.
  • the raw materials for the preparation of the environmentally friendly molluscicide containing iron phosphate chelate include 1 to 80 parts of iron phosphate chelate, 10 to 85 parts of filler, and 1 to 80 parts of iron phosphate chelate. 5 parts binder, 1 to 5 parts lubricant, and 5 to 35 parts water.
  • the raw materials for preparing the environmentally friendly molluscicide containing iron phosphate chelate include 5-15 parts of iron phosphate chelate, 60-80 parts of filler, and 1 to 15 parts of iron phosphate chelate. 5 parts of binder, 1 to 5 parts of lubricant, 0.1 to 1 part of pigment and 5 to 35 parts of water.
  • the raw materials for preparing the environmentally friendly molluscicide containing iron phosphate chelate include 10 parts of iron phosphate chelating agent, 70 parts of filler, and 1 to 5 parts of binding agent. Agent, 1 to 5 parts of lubricant, 0.5 part of pigment and 5 to 35 parts of water.
  • the iron phosphate chelating agent is a chelating product of iron phosphate and a chelating agent.
  • the weight ratio of the iron phosphate to the chelating agent is 1: (0.025-40); preferably, the weight ratio of the iron phosphate to the chelating agent is 1: (0.2 to 5); more preferably Preferably, the weight ratio of the iron phosphate and the chelating agent is 1:(0.8-1.2); more preferably, the weight ratio of the iron phosphate and the chelating agent is 1:1.
  • the chelating agent includes glutamic diacetic acid and its corresponding salt, iminodisuccinic acid and its corresponding salt, dimethylalanine and its corresponding salt, ethylenediamine At least one of disuccinic acid and its corresponding salt and methylglycine diacetic acid and its corresponding salt.
  • the chelating agent includes tetrasodium glutamate diacetate, tetrapotassium glutamate diacetate, tetrasodium iminodisuccinate, tetrapotassium iminodisuccinate, and dicarboxymethylalanine Trisodium salt, tripotassium dicarboxymethylalanine, trisodium ethylenediamine disuccinate, tripotassium ethylenediamine disuccinate, trisodium methylglycine diacetate, and methylglycine diacetic acid At least one of the tripotassium salts.
  • the chelating agent includes glutamate diacetic acid tetrasodium salt, CAS: 51981-21-6.
  • Filler also known as filler, filler or filler
  • filler is a type of solid substance that can be added to a material to improve the performance of the material, or to increase the volume, increase the weight, and reduce the cost of the material.
  • Commonly used industrial fillers are kaolin, diatomaceous earth, talc powder, graphite, carbon black, alumina powder, glass powder, asbestos powder, mica powder, quartz powder, carbon fiber, powdered cork and emery, etc.
  • a large number of fillers are used in plastic processing, rubber processing, paper, coatings, pesticides, and pharmaceuticals in chemical production, which not only improves the performance of these products, but also greatly reduces production costs.
  • the filler includes at least one of corn starch, wheat starch, soybean starch, tapioca starch, and distarch phosphate.
  • the filler is bis-starch phosphate.
  • phosphate bis-starch absorbs water and the phosphate-based charges repel each other, which tends to disperse the molecular chains of the adhesive, which promotes the destruction of the adhesive film on the surface of the closed phosphorous state by the adhesive.
  • the phosphate distarch described in this application was purchased from Suzhou Gaofeng Starch Technology Co., Ltd.
  • Adhesive is one of the most important auxiliary materials, and it is widely used in packaging operations. Adhesives are sticky substances that connect two separate materials together by virtue of their adhesive properties.
  • the adhesive includes at least one of natural wax, chemically modified wax, starch, alginate, agar, lignosulfonate, gum arabic, and modified chitosan ;
  • the modified chitosan is citric acid modified chitosan.
  • the binder includes citric acid modified chitosan.
  • the preparation method of the citric acid-modified chitosan includes: mixing citric acid and sodium hypophosphite with a substance ratio of (5-10):1, adding distilled water to dissolve, and then adding Chitosan is reacted at 100-110°C for 2.5 to 3 hours. After the reaction is completed, it is obtained by ethanol precipitation, washing, suction filtration, drying and grinding.
  • the weight ratio of the chitosan and citric acid is 1:(2 ⁇ 4).
  • the chitosan was purchased from Nanjing Songguan Biotechnology Co., Ltd., CAS: 9012-76-4.
  • the preparation method of the citric acid-modified chitosan includes: placing citric acid and sodium hypophosphite in a ratio of 8:1 in a three-necked flask, and adding a sufficient amount of distilled water Shake well after dissolving completely, weigh the chitosan with a weight ratio of 1:3 to citric acid and add it to a three-necked flask, react at 105°C for 3h, after the reaction, precipitate with ethanol, wash and filter, place Vacuum freeze-drying at -55°C for 36h, and finally grinding and pulverizing to obtain powdered citric acid modified chitosan.
  • citric acid-modified chitosan makes the binding effect moderate. It will not cause the molluscicide to form particles due to the poor binding effect, and it will not cause the molluscicide to agglomerate due to the strong binding effect.
  • citric acid-modified chitosan and the adhesive film on the surface of closed storage phosphorus have higher adsorption activity, and the unique structure of chitosan makes citric acid-modified chitosan It can be adsorbed on the surface of the glue film to the maximum, which is beneficial to destroy the glue film on the surface of the closed storage state and promote the degradation of the residual phosphate in the soil.
  • the water absorption of the citric acid modified chitosan reduces the redox potential of the glue film .
  • the released metal ions play a role, enhance the snail killing effect of the molluscicide, and reduce the residual rate of iron phosphate in the soil.
  • lubricants Agents used to lubricate and reduce frictional resistance are called lubricants.
  • the lubricant includes at least one of magnesium stearate, sodium lauryl sulfate, vegetable oil and hydroxylated vegetable oil; preferably, the lubricant includes hydroxylated vegetable oil.
  • Vegetable oil is a compound formed by the combination of unsaturated fatty acids and glycerin. It is widely distributed in nature. It is the oil obtained from the fruits, seeds and germs of plants, such as peanut oil, soybean oil, linseed oil, castor oil and rapeseed oil.
  • the main components of vegetable oils are esters of straight-chain higher fatty acids and glycerol.
  • fatty acids also contain a variety of unsaturated acids such as erucic acid, tungoleic acid and ricinoleic acid.
  • Vegetable oil mainly contains minerals such as vitamin E, calcium, iron, phosphorus and potassium, and fatty acids. The fatty acids in vegetable oil can make the skin moisturized and shiny.
  • Hydroxylated vegetable oil refers to vegetable oil modified by hydroxyl group.
  • the hydroxylated vegetable oil includes at least one of hydroxylated soybean oil, hydroxylated castor oil, and hydroxylated peanut oil; preferably, the hydroxylated vegetable oil includes hydroxylated soybean oil.
  • the preparation method of the hydroxylated soybean oil includes the following steps:
  • the maleic anhydride accounts for 0.25 to 0.4 wt% of soybean oil; more preferably, the maleic anhydride accounts for 0.34 wt% of soybean oil.
  • the weight ratio of diethylene glycol to soybean oil is (1 ⁇ 1.5):1; more preferably, the weight ratio of diethylene glycol to soybean oil is 1:1.
  • the KOH accounts for 0.04 to 0.09 wt% of the maleic anhydride modified soybean oil; more preferably, the KOH accounts for 0.06 wt% of the maleic anhydride modified soybean oil.
  • soybean oil was purchased from Chongqing Cypress Technology Co., Ltd., CAS: 8001-22-7.
  • the preparation method of the hydroxylated soybean oil includes the following steps:
  • the use of hydroxylated soybean oil can have a higher snail-killing effect in a short time.
  • the probability of salt storage state formation, and hydroxylated soybean oil can chelate iron ions in multiple directions, thereby improving the snail killing effect and reducing the soil residue rate of phosphate.
  • hydroxylated soybean oil makes the snail killer
  • the filler is more uniformly dispersed in the molluscicide, and it may also improve the anorexia caused by the sour taste of the citric acid-modified chitosan, and increase the attraction of the molluscicide to the snails.
  • the weight ratio of the citric acid-modified chitosan and the hydroxylated soybean oil is (0.2-5):1; preferably, the citric acid-modified chitosan and the hydroxylated soybean oil are The weight ratio of citric acid modified chitosan and hydroxylated soybean oil is 1:1; more preferably, the weight ratio of citric acid modified chitosan and hydroxylated soybean oil is 1:1.
  • citric acid-modified chitosan and hydroxylated soybean oil can improve the snail killing effect to a certain extent
  • the applicant found that using both citric acid-modified chitosan and hydroxylated soybean oil at the same time has a much higher effect than when used alone .
  • the weight ratio of citric acid-modified chitosan and hydroxylated soybean oil is (0.2 ⁇ 5): The effect is best when: 1.
  • the citric acid modified chitosan and hydroxylated soybean oil have a certain synergistic effect at a specific weight ratio, and the hydroxylated soybean oil is coated in At the same time as the iron phosphate surface, the force between the citric acid-modified chitosan and the hydroxylated soybean oil makes the citric acid-modified chitosan quickly destroy the gel film on the surface of the closed storage state phosphorus; at the same time, it is hydroxylated
  • the presence of vegetable oil and citric acid-modified chitosan will promote the chelation of tetrasodium glutamate diacetate and iron ions.
  • Glutamate diacetic acid tetrasodium salt is chelated to avoid uneven distribution of chelated iron ions, hinder the molecular movement of iron ions, reduce the chelation rate, and affect the snail killing effect and the soil residual rate of phosphate.
  • citric acid-modified chitosan When the content of citric acid-modified chitosan is too high, too much citric acid-modified chitosan will cause too much anion in the pesticide, and electrostatic repulsion will cause the citric acid-modified chitosan and hydroxylated soybean oil to fail It is well and evenly combined, resulting in defects when destroying the film on the surface of the closed phosphorous, which affects the insecticidal effect and the residual rate of phosphate in the soil.
  • Pigments are raw materials that impart a certain color. People often choose products based on their senses such as sight, touch and smell, and pigments are an important part of vision. Therefore, the proper use of pigments also determines the quality of the product.
  • Synthetic pigments The pigments obtained by chemical synthesis are called synthetic pigments.
  • Inorganic pigments commonly used inorganic pigments include iron oxide, carbon black and chrome oxide green, etc. They have good light resistance and are insoluble in water.
  • Natural pigments Commonly used natural pigments include annatto, cochineal, chlorophyll, curcumin and lutein.
  • the pigment is selected from citrus yellow, curcumin, grape skin red, mulberry red, corn yellow, roselle red, gardenia yellow, cochineal red, golden cherry brown and chrysanthemum yellow extract One or a combination of more.
  • the second aspect of the present application provides a method for preparing an environmentally friendly molluscicide containing iron phosphate chelate, which includes: putting the raw materials of the environmentally friendly molluscicide containing iron phosphate chelate into a pelletizing plate Granules are dried to prepare an environmentally friendly molluscicide containing iron phosphate chelate.
  • the third aspect of this application provides an environmentally friendly molluscicide containing iron phosphate chelate for use in terrestrial and aquatic environments.
  • Example 1 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • its preparation raw materials include 5 parts of iron phosphate chelate, 60 parts of filler, 1 part of binder, 5 parts lubricant, 0.1 part pigment and 29 parts water.
  • the iron phosphate chelate is formed by chelating iron phosphate and a chelating agent; the chelating agent is tetrasodium glutamate diacetate; the weight ratio of the iron phosphate to the chelating agent is 1:0.2; the filling
  • the agent is wheat starch; the binder is citric acid modified chitosan; the lubricant is hydroxylated soybean oil; and the pigment is chamomile yellow.
  • the preparation method of the citric acid-modified chitosan includes: placing citric acid and sodium hypophosphite with a substance ratio of 8:1 in a three-necked flask, adding a sufficient amount of distilled water to completely dissolve it, shaking it, and then weighing Chitosan with a weight ratio of 1:3 to citric acid was added to a three-necked flask and reacted at 105°C for 3 hours. After the reaction was completed, it was precipitated with ethanol, washed and filtered by suction, and vacuum freeze-dried at -55°C for 36 hours. , And finally pulverized to obtain powdered citric acid modified chitosan.
  • the chitosan was purchased from Nanjing Songguan Biotechnology Co., Ltd.
  • the preparation method of the hydroxylated soybean oil includes the following steps:
  • the maleic anhydride accounts for 0.34 wt% of soybean oil; the weight ratio of diethylene glycol to soybean oil is 1:1; and the KOH accounts for 0.06 wt% of maleic anhydride modified soybean oil.
  • the soybean oil was purchased from Chongqing Cypress Technology Co., Ltd.
  • the preparation method of the environmentally friendly molluscicide containing iron phosphate chelate includes: mixing iron phosphate chelate, filler, binder, lubricant, pigment and water uniformly, placing it in a pelletizing tray and making granules.
  • An environmentally friendly molluscicide containing iron phosphate chelate is prepared by drying.
  • Example 2 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • the raw materials for preparation include 15 parts by weight of iron phosphate chelate, 70 parts of filler, 3 parts of binder, 2 parts lubricant, 0.8 parts pigment and 10 parts water.
  • the iron phosphate chelate is formed by chelating iron phosphate and a chelating agent; the chelating agent is tetrasodium glutamate diacetate; the weight ratio of the iron phosphate to the chelating agent is 1:5; the filling
  • the agent is wheat starch; the binder is citric acid modified chitosan; the lubricant is hydroxylated soybean oil; and the pigment is chamomile yellow.
  • the preparation method of the citric acid-modified chitosan includes: placing citric acid and sodium hypophosphite with a substance ratio of 8:1 in a three-necked flask, adding enough distilled water to completely dissolve it, shaking it, and then weighing Chitosan with a weight ratio of 1:3 to citric acid was added to a three-necked flask and reacted at 105°C for 3 hours. After the reaction was completed, it was precipitated with ethanol, washed and filtered by suction, and vacuum freeze-dried at -55°C for 36 hours. , And finally pulverized to obtain powdered citric acid modified chitosan.
  • the chitosan was purchased from Nanjing Songguan Biotechnology Co., Ltd.
  • the preparation method of the hydroxylated soybean oil includes the following steps:
  • the maleic anhydride accounts for 0.34 wt% of soybean oil; the weight ratio of diethylene glycol to soybean oil is 1:1; and the KOH accounts for 0.06 wt% of maleic anhydride modified soybean oil.
  • the soybean oil was purchased from Chongqing Cypress Technology Co., Ltd.
  • the preparation method of the environmentally friendly molluscicide containing iron phosphate chelate includes: mixing iron phosphate chelate, filler, binder, lubricant, pigment and water uniformly, placing it in a pelletizing tray and making granules.
  • the granules of environmentally friendly molluscicide containing iron phosphate chelate are prepared by drying.
  • Example 3 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • the raw materials for preparation include 10 parts of iron phosphate chelate, 70 parts of filler, 3 parts of binder, and parts by weight. 3 parts lubricant, 0.5 parts pigment and 14 parts water.
  • the iron phosphate chelate is formed by chelating iron phosphate and a chelating agent; the chelating agent is tetrasodium glutamate diacetate; the weight ratio of the iron phosphate and the chelating agent is 1:1; the filling
  • the agent is phosphate bis-starch; the binder is citric acid modified chitosan; the lubricant is hydroxylated soybean oil; and the pigment is chamomile yellow.
  • the preparation method of the citric acid-modified chitosan includes: placing citric acid and sodium hypophosphite with a substance ratio of 8:1 in a three-necked flask, adding a sufficient amount of distilled water to completely dissolve it, shaking it, and then weighing Chitosan with a weight ratio of 1:3 to citric acid was added to a three-necked flask and reacted at 105°C for 3 hours. After the reaction was completed, it was precipitated with ethanol, washed and filtered by suction, and vacuum freeze-dried at -55°C for 36 hours. , And finally pulverized to obtain powdered citric acid modified chitosan.
  • the chitosan was purchased from Nanjing Songguan Biotechnology Co., Ltd.
  • the preparation method of the hydroxylated soybean oil includes the following steps:
  • the maleic anhydride accounts for 0.34 wt% of soybean oil; the weight ratio of diethylene glycol to soybean oil is 1:1; and the KOH accounts for 0.06 wt% of maleic anhydride modified soybean oil.
  • the soybean oil was purchased from Chongqing Cypress Technology Co., Ltd.
  • the preparation method of the environmentally friendly molluscicide containing iron phosphate chelate includes: mixing iron phosphate chelate, filler, binder, lubricant, pigment and water uniformly, placing it in a pelletizing tray and making granules.
  • An environmentally friendly molluscicide containing iron phosphate chelate is prepared by drying.
  • Example 4 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • the raw materials for preparation include 1 part of iron phosphate chelate, 60 parts of filler, 1 part of binder, 5 parts lubricant, 0.1 part pigment and 33 parts water.
  • the iron phosphate chelate is formed by chelating iron phosphate and a chelating agent; the chelating agent is tetrasodium glutamate diacetate; the weight ratio of the iron phosphate to the chelating agent is 1:0.025; the filling
  • the agent is wheat starch; the binder is modified chitosan; the modified chitosan is citric acid modified chitosan; the lubricant is hydroxylated soybean oil; the pigment is chamomile yellow .
  • Example 5 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • the raw materials for preparation include 80 parts by weight of iron phosphate chelate, 10 parts of filler, 3 parts of binder, 2 parts lubricant, 0.8 parts pigment and 5 parts water.
  • the iron phosphate chelate is formed by chelating iron phosphate and a chelating agent; the chelating agent is tetrasodium glutamate diacetate; the weight ratio of the iron phosphate to the chelating agent is 1:40; the filling
  • the agent is phosphate double starch; the binder is modified chitosan; the modified chitosan is citric acid modified chitosan; the lubricant is hydroxylated soybean oil; the pigment is glycerin Chrysanthemum yellow.
  • Example 6 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • the specific implementation is the same as that of Example 3, except that the binder is chitosan.
  • Example 7 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • the specific implementation is the same as that of Example 3, except that the citric acid-modified chitosan is malic acid-modified Chitosan.
  • the preparation method of the malic acid-modified chitosan includes: placing malic acid and sodium hypophosphite with a substance ratio of 8:1 in a three-necked flask, adding sufficient distilled water to completely dissolve it, shaking it, and then weighing Chitosan with a weight ratio of 1:3 to malic acid was added to a three-necked flask and reacted at 105°C for 3 hours. After the reaction was completed, it was precipitated with ethanol, washed and filtered by suction, and placed under vacuum freeze-dried at -55°C for 36 hours. , And finally grinding and crushing to obtain powdered malic acid-modified chitosan.
  • Example 8 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate, and its specific implementation is the same as that of Example 3.
  • the method for preparing the citric acid-modified chitosan has the same specific implementation as that of Example 3, except that the weight ratio of the chitosan and citric acid is 1:1.
  • Example 9 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • the specific implementation is the same as that of Example 3, except that the lubricant is soybean oil.
  • Example 10 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • its preparation raw materials include 10 parts of iron phosphate chelate, 70 parts of filler, 18 parts of binder, 3 parts lubricant, 0.5 parts pigment and 14 parts water.
  • Example 11 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • the specific implementation is the same as that of Example 3.
  • the difference is that the environmentally friendly molluscicide containing iron phosphate chelate is
  • the preparation raw materials do not include binders.
  • the preparation method of the environmentally friendly molluscicide containing ferric phosphate chelate includes: mixing ferric phosphate chelate, filler, lubricant, pigment and water uniformly, putting them in a pelletizing tray for granulation, and drying to obtain An environmentally friendly molluscicide of iron phosphate chelate.
  • Example 12 of the present application provides an environmentally friendly molluscicide containing iron phosphate chelate.
  • the specific implementation is the same as that of Example 3.
  • the difference is that the environmentally friendly molluscicide containing iron phosphate chelate is The preparation raw materials do not include lubricants.
  • the preparation method of the environmentally friendly molluscicide containing ferric phosphate chelate includes: mixing ferric phosphate chelate, filler, binder, pigment and water uniformly, putting them in a pelletizing tray for granulation, and drying to prepare An environmentally friendly molluscicide containing iron phosphate chelate. Performance evaluation
  • Insect prevention effect and molluscicide on crop safety test the insect control effect of the environmentally friendly molluscicide obtained in Examples 1-12 and the environmentally friendly molluscicide obtained in Examples 1 to 5 on crop safety test according to GB/T17980.
  • the 69-2004 standard was tested, and the dosage was 3333.5 g/mu; the insect control effect test recorded the control effect on the 3rd, 7th, 14th and 21st day.
  • Soil residue test of iron phosphate chelate After applying the environmentally friendly molluscicide obtained in Examples 1-12, the amount of iron phosphate chelate residue in the soil of the molluscicide was tested;
  • experimental crop is cabbage; the soil is sandy loam with an area of 20 square meters;
  • Implementation method 1. Take 1 gram of soil sample per 4 square meters and mix to determine the initial soil sample; 2. Spread 200 grams of environmentally friendly molluscicide containing iron phosphate chelate per square meter; take 1 per 4 square meters after 3.21 days Gram soil sample, mix, determine the final sample; 4. Atomic absorption method to determine the iron content in the initial and final soil samples.
  • Safety test for the applicator When applying the environmentally friendly molluscicide obtained in Examples 1 to 5, record whether the molluscicide has an impact on the applicator; if the applicator does not have any physical discomfort during the application, If there is no erythema or redness on the skin, it means that the molluscicide has no effect on the person applying the medicine.

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Abstract

本申请涉及软体动物防治领域，更具体地，本申请涉及一种含有磷酸铁螯合物的环保杀螺剂及其制备方法。所述含有磷酸铁螯合剂的环保杀螺剂的制备原料包括磷酸铁螯合物、填充剂和水；所述填充剂包括玉米淀粉、小麦淀粉、大豆淀粉、木薯淀粉和磷酸酯双淀粉中的至少一种，优选为磷酸酯双淀粉。本申请提供的杀螺剂对人类和水生生物无害，对宠物和野生动物无害，同时能够改善磷酸铁在土壤中的溶解性，使其作为磷肥被作物吸收，既解决了磷酸铁在土壤中的降解残留问题，又给予了作物养分，保证了该杀螺剂对生态环境的无害性和安全性。本申请提供的杀螺剂解决了多数杀螺产品对鱼类等水生生物及野生动物有毒有害、残留高以及土壤降解差等环境生态污染的问题。

Description

一种含有磷酸铁螯合物的环保杀螺剂及其制备方法 技术领域
本申请涉及软体动物防治领域，更具体地，本申请涉及一种含有磷酸铁螯合物的环保杀螺剂及其制备方法。
背景技术
危害农作物的软体动物主要有蜗牛(俗称水牛儿或旱螺蛳)、蛞蝓、田螺(俗称螺蛳)、福寿螺及钉螺。软体动物发生量大，蜗牛雌雄同体，一次产卵可达300只，一年可产卵300～2000只；福寿螺雌雄异体，每只雌螺一次可产卵200～500只，每只卵50天即可成熟繁殖，可在田间出现叠代现象。蜗牛和田螺食性贪婪，咬食农作物的幼芽、嫩叶和嫩茎，并可导致根部、茎部和叶片出现大量伤口，利于真菌、细菌和病毒等病原菌的侵入，使作物危害程度加重。软体动物广泛分布于世界上潮湿温暖的地区，严重危害到园艺、谷物、水果、蔬菜、棉花和烟草等等作物。其中更为严重的是钉螺，是血吸虫的唯一中间宿主，是血吸虫病传播中不可缺少的环节。
杀螺胺、杀螺胺乙醇铵盐和四聚乙醛是目前杀螺剂的主要品种。然而杀螺胺及乙醇铵盐对鱼类、蛙类和贝类等水生生物高毒，污染水体极易造成药害；因其毒性较强并且残留高，也禁止在蔬菜、水果和园艺上使用，主要用于杀灭钉螺和水稻上防治福寿螺，故而使用范围较窄。同时在使用中，干粉及浓溶液对人体粘膜有刺激作用，能引起流泪、眼刺痛、鼻塞、流涕咽喉干痛及声音嘶哑等症状。四聚乙醛虽对水生生物低毒，但急性毒性较强，对鸟类等野生动物有害，难溶于水，在土壤中降解性不好，目前已有英国报道，发现地下水体中四聚乙醛残留超标。因此，需要提供一种对人类、水生生物和野生动物安全低毒的杀螺剂，并在土壤中具备较好的溶解性，易于被植物吸收，从而不会在土壤中大量集聚，造成土壤生态问题。
发明内容
针对现有技术中存在的一些问题，本申请第一个方面提供了一种含有磷酸铁螯合物的环保杀螺剂，其制备原料包括磷酸铁螯合物、填充剂和水；所述填充剂包括玉米淀粉、小麦淀粉、大豆淀粉、木薯淀粉和磷酸酯双淀粉中的至少一种，优选为磷酸酯双淀粉。
作为本申请的一种优选技术方案，所述含有磷酸铁螯合物的环保杀螺剂的制备原料还包括粘合剂；所述粘合剂包括天然蜡、经化学改性的蜡、淀粉、藻酸盐、琼脂、木质素磺酸盐、阿拉伯树胶和改性壳聚糖中的至少一种，优选为改性壳聚糖。
作为本申请的一种优选技术方案，所述改性壳聚糖为柠檬酸改性壳聚糖。
作为本申请的一种优选技术方案，所述含有磷酸铁螯合物的环保杀螺剂的制备原料还 包括润滑剂；所述润滑剂包括硬脂酸镁、十二烷基硫酸钠、植物油和羟基化植物油中的至少一种，优选为羟基化植物油。
作为本申请的一种优选技术方案，所述磷酸铁螯合物由磷酸铁和螯合剂螯合而成；所述磷酸铁和螯合剂的重量比为1:(0.025～40)。
作为本申请的一种优选技术方案，所述磷酸铁和螯合剂的重量比为1:(0.2～5)，优选为1:(0.8～1.2)。
作为本申请的一种优选技术方案，所述螯合剂包括谷氨酸二乙酸及其对应的盐、亚氨基二琥珀酸及其对应的盐、二羧甲基丙氨酸及其对应的盐、乙二胺二琥珀酸及其对应的盐以及甲基甘氨酸二乙酸及其对应的盐中的至少一种。
作为本申请的一种优选技术方案，所述柠檬酸改性壳聚糖和羟基化植物油的重量比为(0.2～5):1，优选为(0.2～1.5):1。
本申请的第二个方面提供了一种含有磷酸铁螯合物的环保杀螺剂的制备方法，其包括：将含有磷酸铁螯合物的环保杀螺剂的制备原料放入造粒盘造粒，经干燥制得含有磷酸铁螯合物的环保杀螺剂。
本申请第三个方面提供了一种含有磷酸铁螯合物的环保杀螺剂应用于陆生环境和水生环境中。
本申请与现有技术相比具有以下有益效果：
本申请提供的杀螺剂对人类和水生生物无害，对宠物和野生动物无害，同时能够改善磷酸铁在土壤中的溶解性，使其作为磷肥被作物吸收，既解决了磷酸铁在土壤中的降解残留问题，又给予了作物养分，保证了该杀螺剂对生态环境的无害性和安全性。
具体实施方式
以下通过具体实施方式说明本申请，但不局限于以下给出的具体实施例。
本申请第一个方面提供了一种含有磷酸铁螯合物的环保杀螺剂，其制备原料包括磷酸铁螯合物、填充剂和水。
在一种实施方式中，所述含有磷酸铁螯合物的环保杀螺剂的制备原料还包括粘合剂。
在一种实施方式中，所述含有磷酸铁螯合物的环保杀螺剂的制备原料还包括润滑剂。
在一种实施方式中，所述含有磷酸铁螯合物的环保杀螺剂的制备原料还包括色素。
在一种优选的实施方式中，按重量份计，所述含有磷酸铁螯合物的环保杀螺剂的制备原料包括1～80份磷酸铁螯合物、10～85份填充剂、1～5份粘合剂、1～5份润滑剂和5～35份水。
在一种优选的实施方式中，按重量份计，所述含有磷酸铁螯合物的环保杀螺剂的制备原料包括5～15份磷酸铁螯合物、60～80份填充剂、1～5份粘合剂、1～5份润滑剂、0.1～ 1份色素和5～35份水。
在一种更优选的实施方式中，按重量份计，所述含有磷酸铁螯合物的环保杀螺剂的制备原料包括10份磷酸铁螯合剂、70份填充剂、1～5份粘合剂、1～5份润滑剂、0.5份色素和5～35份水。
磷酸铁螯合剂
磷酸铁螯合剂为磷酸铁和螯合剂螯合的形成物。
在一种实施方式中，所述磷酸铁和螯合剂的重量比为1:(0.025～40)；优选地，所述磷酸铁和螯合剂的重量比为1:(0.2～5)；进一步优选地，所述磷酸铁和螯合剂的重量比为1:(0.8～1.2)；更优选地，所述磷酸铁和螯合剂的重量比为1:1。
在一种实施方式中，所述螯合剂包括谷氨酸二乙酸及其对应的盐、亚氨基二琥珀酸及其对应的盐、二羧甲基丙氨酸及其对应的盐、乙二胺二琥珀酸及其对应的盐以及甲基甘氨酸二乙酸及其对应的盐中的至少一种。
优选地，所述螯合剂包括谷氨酸二乙酸四钠盐、谷氨酸二乙酸四钾盐、亚氨基二琥珀酸四钠盐、亚氨基二琥珀酸四钾盐、二羧甲基丙氨酸三钠盐、二羧甲基丙氨酸三钾盐、乙二胺二琥珀酸三钠盐、乙二胺二琥珀酸三钾盐、甲基甘氨酸二乙酸三钠盐以及甲基甘氨酸二乙酸三钾盐中的至少一种。
更优选地，所述螯合剂包括谷氨酸二乙酸四钠盐，CAS:51981-21-6。
填充剂
填充剂又名填料、填加剂或填充物，是一类加入物料中可以改善物料性能，或能增容、增重、并降低物料的成本的固体物质。常用的工业填充剂有高岭土、硅藻土、滑石粉、石墨、炭黑、氧化铝粉、玻璃粉、石棉粉、云母粉、石英粉、碳纤维、粉末状软木和金刚砂等。在化工生产的塑料加工、橡胶加工、纸张、涂料、农药和医药等产品中大量使用各种填充剂，不但改善了这些产品的性能，也大大降低了生产成本。
在一种实施方式中，所述填充剂包括玉米淀粉、小麦淀粉、大豆淀粉、木薯淀粉和磷酸酯双淀粉中的至少一种。
优选地，所述填充剂为磷酸酯双淀粉。
申请人意外地发现同时使用磷酸酯双淀粉和粘合剂，可以起到协同增效的作用，使得粘合剂更容易对闭蓄态磷表面胶膜产生破坏，降低了土壤残余率。申请人认为可能的原因是磷酸酯双淀粉吸水，磷酸基电荷相互排斥，使得粘合剂分子链之间趋于分散的趋势，促进粘合剂对闭蓄态磷表面胶膜的破坏。
本申请所述磷酸酯双淀粉购自苏州高峰淀粉科技有限公司。
粘合剂
粘合剂是最重要的辅助材料之一，在包装作业中应用极为广泛。粘合剂是具有粘性的物质，借助其粘性能将两种分离的材料连接在一起。
在一种实施方式中，所述粘合剂包括天然蜡、经化学改性的蜡、淀粉、藻酸盐、琼脂、木质素磺酸盐、阿拉伯树胶和改性壳聚糖中的至少一种；优选地，所述改性壳聚糖为柠檬酸改性壳聚糖。
在一种实施方式中，所述粘合剂包括柠檬酸改性壳聚糖。
在一种实施方式中，所述柠檬酸改性壳聚糖的制备方法包括：将物质的量比为(5～10):1的柠檬酸和次亚磷酸钠混合，加入蒸馏水溶解，之后加入壳聚糖，100～110℃下反应2.5～3h，反应结束后，用乙醇沉淀、洗涤、抽滤、干燥并且研磨即得。
优选地，所述壳聚糖和柠檬酸的重量比为1:(2～4)。
所述壳聚糖购自南京松冠生物科技有限公司，CAS:9012-76-4。
在一种优选的实施方式中，所述柠檬酸改性壳聚糖的制备方法包括：将物质的量比为8:1的柠檬酸和次亚磷酸钠置于三口烧瓶中，加入足量蒸馏水完全溶解后摇匀，再称取与柠檬酸的重量比为1:3的壳聚糖加入三口烧瓶中，在105℃下反应3h，反应结束后，用乙醇沉淀、洗涤并抽滤，置于-55℃条件下真空冷冻干燥36h，最后研磨粉碎制得粉末状的柠檬酸改性壳聚糖。
申请人发现选用特定的粘合剂柠檬酸改性壳聚糖时能够改善粘合剂的粘合效果、提高杀螺剂的杀螺效果并且快速降低磷酸盐的土壤残留率，申请人认为可能的原因是柠檬酸改性壳聚糖使得粘合效果适中，既不会因为粘合效果太差导致无法使杀螺剂形成颗粒，也不会因为粘合效果太强，出现杀螺剂结块现象，导致杀螺剂对于螺类的引诱力下降；柠檬酸改性壳聚糖与闭蓄态磷表面的胶膜的吸附活性较高，同时壳聚糖特有的结构使得柠檬酸改性壳聚糖能够最大限度地吸附在胶膜表面，有利于破坏闭蓄态磷表面的胶膜，促进土壤中残留的磷酸盐降解，同时柠檬酸改性壳聚糖的吸水性降低了胶膜的氧化还原电位，促进闭蓄态磷表面胶膜的还原，使得释放出来的金属离子发挥作用，增强了杀螺剂的杀螺效果，降低了磷酸铁在土壤中的残留率。
润滑剂
用以润滑和降低摩擦阻力的试剂称为润滑剂。
在一种实施方式中，所述润滑剂包括硬脂酸镁、十二烷基硫酸钠、植物油和羟基化植物油中的至少一种；优选地，所述润滑剂包括羟基化植物油。
植物油是由不饱和脂肪酸和甘油化合而成的化合物，广泛分布于自然界中，是从植物的果实、种子和胚芽中得到的油脂，如花生油、豆油、亚麻油、蓖麻油和菜子油等。植物油的主要成分是直链高级脂肪酸和甘油生成的酯，脂肪酸除软脂酸、硬脂酸和油酸外，还 含有多种不饱和酸，如芥酸、桐油酸和蓖麻油酸等。植物油主要含有维生素E、钙、铁、磷和钾等矿物质以及脂肪酸等。植物油中的脂肪酸能使皮肤滋润有光泽。
羟基化植物油指的是对植物油进行羟基改性的植物油。
在一种实施方式中，所述羟基化植物油包括羟基化大豆油、羟基化蓖麻油和羟基化花生油中的至少一种；优选地，所述羟基化植物油包括羟基化大豆油。
在一种实施方式中，所述羟基化大豆油的制备方法包括下面步骤：
(1)在四口烧瓶中加入大豆油和马来酸酐，加热升温至190～210℃，反应2～3h，得到中间体马来酸酐改性大豆油；
(2)在四口烧瓶中加入马来酸酐改性大豆油、二甘醇和KOH，加热升温至190～220℃，反应5～6h，得到粗羟基化大豆油；
(3)在四口烧瓶中加入粗羟基化大豆油，通过多次水洗和分液除去未反应的二甘醇；加入3wt％的水，以及质量浓度为98％的磷酸以中和KOH，0.3wt％的硅酸镁吸附剂，减压蒸馏将水除去，通过抽滤将吸附剂和钾盐除去。
优选地，所述马来酸酐占大豆油的0.25～0.4wt％；更优选地，所述马来酸酐占大豆油的0.34wt％。
优选地，所述二甘醇和大豆油的重量比为(1～1.5):1；更优选地，所述二甘醇和大豆油的重量比为1:1。
优选地，所述KOH占马来酸酐改性大豆油的0.04～0.09wt％；更优选地，所述KOH占马来酸酐改性大豆油的0.06wt％。
所述大豆油购自重庆赛普那斯科技有限公司，CAS:8001-22-7。
在一种优选的实施方式中，所述羟基化大豆油的制备方法包括下面步骤：
(1)在四口烧瓶中加入大豆油及马来酸酐，将四口瓶置于加热套中，安装好搅拌、冷凝水、温度计和氮气保护。开启氮气保护、冷凝水及搅拌，加热套升温至210℃，反应3h，得到中间体马来酸酐改性大豆油；
(2)在四口烧瓶中加入马来酸酐改性大豆油、二甘醇和KOH，将混合物置于加热套中，安装好搅拌、冷凝水、温度计和氮气保护，其中，冷凝水应水平安装，以便排出反应过程中产生的水。开启氮气保护、冷凝水及搅拌，加热套升温至220℃，反应6h，得到粗羟基化大豆油；
(3)在四口烧瓶中加入粗羟基化大豆油，通过多次水洗和分液除去未反应的二甘醇；加入3wt％的水，以及质量浓度为98w％的磷酸以中和KOH，0.3wt％的硅酸镁吸附剂，减压蒸馏将水除去，通过抽滤将吸附剂和钾盐除去。
申请人在实验中发现选用特定的润滑剂可以进一步提高杀螺效果以及降低土壤中磷酸 盐的残留率。使用羟基化大豆油可以在短时间内具有一个较高的杀螺效果，申请人认为可能的原因是羟基化大豆油中较长的碳链能够对磷酸盐进行一定程度的包覆作用，降低磷酸盐闭蓄态形成的几率，同时羟基化大豆油可以对铁离子进行多方位的螯合，从而提高杀螺效果以及降低磷酸盐的土壤残留率，另一方面羟基化大豆油使得杀螺剂中填充剂更为均匀地分散在杀螺剂中，还可能改善螺类因柠檬酸改性壳聚糖带来的酸味所导致的厌食性，增加了杀螺剂对螺类的引诱力。
在一种实施方式中，所述柠檬酸改性壳聚糖和羟基化大豆油的重量比为(0.2～5):1；优选地，所述柠檬酸改性壳聚糖和羟基化大豆油的重量比为(0.2～1.5):1；更优选地，所述柠檬酸改性壳聚糖和羟基化大豆油的重量比为1:1。
虽然柠檬酸改性壳聚糖和羟基化大豆油的存在可以在一定程度上提高杀螺的效果，申请人发现同时使用柠檬酸改性壳聚糖和羟基化大豆油比单一使用时效果大大增高。同时申请人发现在同时使用柠檬酸改性壳聚糖和羟基化大豆油时需要严格控制它们之间的重量比，当柠檬酸改性壳聚糖与羟基化大豆油的重量比为(0.2～5):1时效果最好，申请人猜测可能的原因是在特定的重量比下柠檬酸改性壳聚糖与羟基化大豆油具有一定的协同增效的作用，羟基化大豆油包覆在磷酸铁盐表面的同时，柠檬酸改性壳聚糖和羟基化大豆油之间的作用力使得柠檬酸改性壳聚糖快速将形成的闭蓄态磷表面的胶膜破坏掉；同时羟基化植物油和柠檬酸改性壳聚糖的存在会促进谷氨酸二乙酸四钠盐与铁离子的螯合，它们之间与铁离子螯合的位点强弱不同，使得铁离子持续缓慢地与谷氨酸二乙酸四钠盐螯合，避免螯合的铁离子分布不均，阻碍铁离子的分子移动，降低螯合率，影响杀螺效果和磷酸盐的土壤残留率。当柠檬酸改性壳聚糖含量过高时，柠檬酸改性壳聚糖过多导致杀虫剂中的阴离子过多，静电斥力导致柠檬酸改性壳聚糖和羟基化大豆油之间不能很好均匀地结合在一起，导致在破坏闭蓄态磷表面的胶膜时存在缺陷，影响杀虫效果和磷酸盐的土壤残余率。
色素
色素是赋予一定颜色的原料。人们选择商品往往凭视、触和嗅等感觉，而色素是视觉方面的重要一环，因此色素用得是否适当对制品好坏也起决定作用。(1)合成色素：化工合成制得的色素称合成色素。(2)无机色素：常用的无机色素有氧化铁、碳黑和氧化铬绿等，它们具有良好的耐光性，不溶于水。(3)天然色素：常用的天然色素有胭脂树红、胭脂虫红、叶绿素、姜黄素和叶红素等。
在一种实施方式中，所述色素选自柑橘黄、姜黄素、葡萄皮红、桑椹红、玉米黄、玫瑰茄红、栀子黄、胭脂虫红、金樱子棕和菊花黄浸膏中的一种或多种的组合。
本申请的第二个方面提供了一种含有磷酸铁螯合物的环保杀螺剂的制备方法，其包括：将含有磷酸铁螯合物的环保杀螺剂的制备原料放入造粒盘造粒，经干燥制得含有磷酸铁螯 合物的环保杀螺剂。
本申请第三个方面提供了一种含有磷酸铁螯合物的环保杀螺剂应用于陆生环境和水生环境中。
实施例
在下文中，通过实施例对本申请进行更详细地描述，但应理解，这些实施例仅仅是示例的而非限制性的。如果没有其它说明，下面实施例所用原料都是市售的。
实施例1
本申请的实施例1提供了一种含有磷酸铁螯合物的环保杀螺剂，按重量份计，其制备原料包括5份磷酸铁螯合物、60份填充剂、1份粘合剂、5份润滑剂、0.1份色素和29份水。
所述磷酸铁螯合物为磷酸铁和螯合剂螯合而成；所述螯合剂为谷氨酸二乙酸四钠盐；所述磷酸铁和螯合剂的重量比为1:0.2；所述填充剂为小麦淀粉；所述粘合剂为柠檬酸改性壳聚糖；所述润滑剂为羟基化大豆油；所述色素为甘菊黄。
所述柠檬酸改性壳聚糖的制备方法包括：将物质的量比为8:1的柠檬酸和次亚磷酸钠置于三口烧瓶中，加入足量蒸馏水完全溶解后摇匀，再称取与柠檬酸的重量比为1:3的壳聚糖加入三口烧瓶中，在105℃下反应3h，反应结束后，用乙醇沉淀、洗涤并抽滤，置于-55℃条件下真空冷冻干燥36h，最后研磨粉碎制得粉末状的柠檬酸改性壳聚糖。
所述壳聚糖购自南京松冠生物科技有限公司。
所述羟基化大豆油的制备方法包括下面步骤：
(1)在四口烧瓶中加入大豆油及马来酸酐，将四口瓶置于加热套中，安装好搅拌、冷凝水、温度计和氮气保护。开启氮气保护、冷凝水及搅拌，加热套升温至210℃，反应3h，得到中间体马来酸酐改性大豆油；
(2)在四口烧瓶中加入马来酸酐改性大豆油、二甘醇和KOH，将混合物置于加热套中，安装好搅拌、冷凝水、温度计和氮气保护，其中，冷凝水应水平安装，以便排出反应过程中产生的水。开启氮气保护、冷凝水及搅拌，加热套升温至220℃，反应6h，得到粗羟基化大豆油；
(3)在四口烧瓶中加入粗羟基化大豆油，通过多次水洗和分液除去未反应的二甘醇；加入3wt％的水，以及质量浓度为98w％的磷酸以中和KOH，0.3wt％的硅酸镁吸附剂，减压蒸馏将水除去，通过抽滤将吸附剂和钾盐除去。
所述马来酸酐占大豆油的0.34wt％；所述二甘醇与大豆油的重量比为1:1；所述KOH占马来酸酐改性大豆油的0.06wt％。
所述大豆油购自重庆赛普那斯科技有限公司。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法包括：将磷酸铁螯合物、填充剂、粘合剂、润滑剂、色素和水混合均匀，放入造粒盘造粒，经干燥制得含有磷酸铁螯合物的环保杀螺剂。
实施例2
本申请的实施例2提供了一种含有磷酸铁螯合物的环保杀螺剂，按重量份计，其制备原料包括15份磷酸铁螯合物、70份填充剂、3份粘合剂、2份润滑剂、0.8份色素和10份水。
所述磷酸铁螯合物为磷酸铁和螯合剂螯合而成；所述螯合剂为谷氨酸二乙酸四钠盐；所述磷酸铁和螯合剂的重量比为1:5；所述填充剂为小麦淀粉；所述粘合剂为柠檬酸改性壳聚糖；所述润滑剂为羟基化大豆油；所述色素为甘菊黄。
所述柠檬酸改性壳聚糖的制备方法包括：将物质的量比为8:1的柠檬酸和次亚磷酸钠置于三口烧瓶中，加入足量蒸馏水完全溶解后摇匀，再称取与柠檬酸的重量比为1:3的壳聚糖加入三口烧瓶中，在105℃下反应3h，反应结束后，用乙醇沉淀、洗涤并抽滤，置于-55℃条件下真空冷冻干燥36h，最后研磨粉碎制得粉末状的柠檬酸改性壳聚糖。
所述壳聚糖购自南京松冠生物科技有限公司。
所述羟基化大豆油的制备方法包括下面步骤：
(1)在四口烧瓶中加入大豆油及马来酸酐，将四口瓶置于加热套中，安装好搅拌、冷凝水、温度计和氮气保护。开启氮气保护、冷凝水及搅拌，加热套升温至210℃，反应3h，得到中间体马来酸酐改性大豆油；
(2)在四口烧瓶中加入马来酸酐改性大豆油、二甘醇和KOH，将混合物置于加热套中，安装好搅拌、冷凝水、温度计和氮气保护，其中，冷凝水应水平安装，以便排出反应过程中产生的水。开启氮气保护、冷凝水及搅拌，加热套升温至220℃，反应6h，得到粗羟基化大豆油；
(3)在四口烧瓶中加入粗羟基化大豆油，通过多次水洗、分液除去未反应的二甘醇；加入3wt％的水，以及质量浓度为98w％的磷酸以中和KOH，0.3wt％的硅酸镁吸附剂，减压蒸馏将水除去，通过抽滤将吸附剂和钾盐除去。
所述马来酸酐占大豆油的0.34wt％；所述二甘醇与大豆油的重量比为1:1；所述KOH占马来酸酐改性大豆油的0.06wt％。
所述大豆油购自重庆赛普那斯科技有限公司。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法包括：将磷酸铁螯合物、填充剂、粘合剂、润滑剂、色素和水混合均匀，放入造粒盘造粒，经干燥制得含有磷酸铁螯合物的环保杀螺剂的颗粒。
实施例3
本申请的实施例3提供了一种含有磷酸铁螯合物的环保杀螺剂，按重量份计，其制备原料包括10份磷酸铁螯合物、70份填充剂、3份粘合剂、3份润滑剂、0.5份色素和14份水。
所述磷酸铁螯合物为磷酸铁和螯合剂螯合而成；所述螯合剂为谷氨酸二乙酸四钠盐；所述磷酸铁和螯合剂的重量比为1:1；所述填充剂为磷酸酯双淀粉；所述粘合剂为柠檬酸改性壳聚糖；所述润滑剂为羟基化大豆油；所述色素为甘菊黄。
所述柠檬酸改性壳聚糖的制备方法包括：将物质的量比为8:1的柠檬酸和次亚磷酸钠置于三口烧瓶中，加入足量蒸馏水完全溶解后摇匀，再称取与柠檬酸的重量比为1:3的壳聚糖加入三口烧瓶中，在105℃下反应3h，反应结束后，用乙醇沉淀、洗涤并抽滤，置于-55℃条件下真空冷冻干燥36h，最后研磨粉碎制得粉末状的柠檬酸改性壳聚糖。
所述壳聚糖购自南京松冠生物科技有限公司。
所述羟基化大豆油的制备方法包括下面步骤：
(1)在四口烧瓶中加入大豆油及马来酸酐，将四口瓶置于加热套中，安装好搅拌、冷凝水、温度计和氮气保护。开启氮气保护、冷凝水及搅拌，加热套升温至210℃，反应3h，得到中间体马来酸酐改性大豆油；
(2)在四口烧瓶中加入马来酸酐改性大豆油、二甘醇和KOH，将混合物置于加热套中，安装好搅拌、冷凝水、温度计和氮气保护，其中，冷凝水应水平安装，以便排出反应过程中产生的水。开启氮气保护、冷凝水及搅拌，加热套升温至220℃，反应6h，得到粗羟基化大豆油；
(3)在四口烧瓶中加入粗羟基化大豆油，通过多次水洗、分液除去未反应的二甘醇；加入3wt％的水，以及质量浓度为98w％的磷酸以中和KOH，0.3wt％的硅酸镁吸附剂，减压蒸馏将水除去，通过抽滤将吸附剂和钾盐除去。
所述马来酸酐占大豆油的0.34wt％；所述二甘醇与大豆油的重量比为1:1；所述KOH占马来酸酐改性大豆油的0.06wt％。
所述大豆油购自重庆赛普那斯科技有限公司。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法包括：将磷酸铁螯合物、填充剂、粘合剂、润滑剂、色素和水混合均匀，放入造粒盘造粒，经干燥制得含有磷酸铁螯合物的环保杀螺剂。
实施例4
本申请的实施例4提供了一种含有磷酸铁螯合物的环保杀螺剂，按重量份计，其制备原料包括1份磷酸铁螯合物、60份填充剂、1份粘合剂、5份润滑剂、0.1份色素和33份 水。
所述磷酸铁螯合物为磷酸铁和螯合剂螯合而成；所述螯合剂为谷氨酸二乙酸四钠盐；所述磷酸铁和螯合剂的重量比为1:0.025；所述填充剂为小麦淀粉；所述粘合剂为改性壳聚糖；所述改性壳聚糖为柠檬酸改性壳聚糖；所述润滑剂为羟基化大豆油；所述色素为甘菊黄。
所述柠檬酸改性壳聚糖的制备方法其具体实施方式同实施例3。
所述羟基化大豆油的制备方法其具体实施方式同实施例3。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法其具体实施方式同实施例3。
实施例5
本申请的实施例5提供了一种含有磷酸铁螯合物的环保杀螺剂，按重量份计，其制备原料包括80份磷酸铁螯合物、10份填充剂、3份粘合剂、2份润滑剂、0.8份色素和5份水。
所述磷酸铁螯合物为磷酸铁和螯合剂螯合而成；所述螯合剂为谷氨酸二乙酸四钠盐；所述磷酸铁和螯合剂的重量比为1:40；所述填充剂为磷酸酯双淀粉；所述粘合剂为改性壳聚糖；所述改性壳聚糖为柠檬酸改性壳聚糖；所述润滑剂为羟基化大豆油；所述色素为甘菊黄。
所述柠檬酸改性壳聚糖的制备方法其具体实施方式同实施例3。
所述羟基化大豆油的制备方法其具体实施方式同实施例3。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法其具体实施方式同实施例3。
实施例6
本申请的实施例6提供了一种含有磷酸铁螯合物的环保杀螺剂，其具体实施方式同实施例3，不同之处在于，所述粘合剂为壳聚糖。
所述羟基化大豆油的制备方法其具体实施方式同实施例3。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法其具体实施方式同实施例3。
实施例7
本申请的实施例7提供了一种含有磷酸铁螯合物的环保杀螺剂，其具体实施方式同实施例3，不同之处在于，所述柠檬酸改性壳聚糖为苹果酸改性壳聚糖。
所述苹果酸改性壳聚糖的制备方法包括：将物质的量比为8:1的苹果酸和次亚磷酸钠置于三口烧瓶中，加入足量蒸馏水完全溶解后摇匀，再称取与苹果酸的重量比为1:3的壳聚糖加入三口烧瓶中，在105℃下反应3h，反应结束后，用乙醇沉淀、洗涤并抽滤，置于-55℃条件下真空冷冻干燥36h，最后研磨粉碎制得粉末状的苹果酸改性壳聚糖。
所述羟基化大豆油的制备方法其具体实施方式同实施例3。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法其具体实施方式同实施例3。
实施例8
本申请的实施例8提供了一种含有磷酸铁螯合物的环保杀螺剂，其具体实施方式同实施例3。
所述柠檬酸改性壳聚糖的制备方法，其具体实施方式同实施例3，不同之处在于，所述壳聚糖和柠檬酸的重量比为1:1。
所述羟基化大豆油的制备方法其具体实施方式同实施例3。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法其具体实施方式同实施例3。
实施例9
本申请的实施例9提供了一种含有磷酸铁螯合物的环保杀螺剂，其具体实施方式同实施例3，不同之处在于，所述润滑剂为大豆油。
所述柠檬酸改性壳聚糖的制备方法其具体实施方式同实施例3。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法其具体实施方式同实施例3。
实施例10
本申请的实施例10提供了一种含有磷酸铁螯合物的环保杀螺剂，按重量份计，其制备原料包括10份磷酸铁螯合物、70份填充剂、18份粘合剂、3份润滑剂、0.5份色素和14份水。
所述柠檬酸改性壳聚糖的制备方法其具体实施方式同实施例3。
所述羟基化大豆油的制备方法其具体实施方式同实施例3。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法其具体实施方式同实施例3。
实施例11
本申请的实施例11提供了一种含有磷酸铁螯合物的环保杀螺剂，其具体实施方式同实施例3，不同之处在于，所述含有磷酸铁螯合物的环保杀螺剂的制备原料不包括粘合剂。
所述羟基化大豆油的制备方法其具体实施方式同实施例3。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法包括：将磷酸铁螯合物、填充剂、润滑剂、色素和水混合均匀，放入造粒盘造粒，经干燥制得含有磷酸铁螯合物的环保杀螺剂。
实施例12
本申请的实施例12提供了一种含有磷酸铁螯合物的环保杀螺剂，其具体实施方式同实施例3，不同之处在于，所述含有磷酸铁螯合物的环保杀螺剂的制备原料不包括润滑剂。
所述柠檬酸改性壳聚糖的制备方法其具体实施方式同实施例3。
所述含有磷酸铁螯合物的环保杀螺剂的制备方法包括：将磷酸铁螯合物、填充剂、粘合剂、色素和水混合均匀，放入造粒盘造粒，经干燥制得含有磷酸铁螯合物的环保杀螺剂。 性能评估
1.防虫效果与杀螺剂对作物安全性测试：实施例1～12得到的环保杀螺剂的防虫效果和实施例1～5得到的环保杀螺剂对作物安全性测试按照GB/T17980.69-2004标准进行测试，使用剂量为3333.5克/亩；防虫效果测试记录第3天、第7天、地14天和第21天的防治效果。
2.磷酸铁螯合物的土壤残留测试：施用实施例1～12得到的环保杀螺剂后杀螺剂中磷酸铁螯合物在土壤残留量进行测试；
实验条件：实验作物为甘蓝；土壤为面积为20平米的沙壤土；
实施方法：1.每4平米取1克土壤样，混合，确定土壤初样；2.每平方米均匀撒施200克含有磷酸铁螯合物的环保杀螺剂；3.21天后每4平米取1克土壤样，混合，确定终样；4.原子吸收法测定土壤初样和终样中的铁含量。
3.对施药人安全性测试：在施用实施例1～5得到的环保杀螺剂时记录杀螺剂对施药人是否产生影响；若施药人在施药时无任何身体不适感，皮肤未出现红斑、红肿，则表示杀螺剂对施药人无影响。
表1
Figure PCTCN2019129756-appb-000001
从表1的性能测试结果中可知本申请提供的含有磷酸铁螯合物的环保杀螺剂短期内具有很好的杀螺效果，同时对农作物无任何药害，对施药人无任何影响，磷酸铁在土壤中无残留，符合绿色发展的需要。
前述的实例仅是说明性的，用于解释本申请所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本申请的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (10)

  1. 一种含有磷酸铁螯合物的环保杀螺剂，其特征在于，其制备原料包括磷酸铁螯合物、填充剂和水；所述填充剂包括玉米淀粉、小麦淀粉、大豆淀粉、木薯淀粉和磷酸酯双淀粉中的至少一种，优选为磷酸酯双淀粉。
  2. 根据权利要求1所述含有磷酸铁螯合物的环保杀螺剂，其特征在于，所述含有磷酸铁螯合物的环保杀螺剂的制备原料还包括粘合剂；所述粘合剂包括天然蜡、经化学改性的蜡、淀粉、藻酸盐、琼脂、木质素磺酸盐、阿拉伯树胶和改性壳聚糖中的至少一种，优选为改性壳聚糖。
  3. 根据权利要求2所述含有磷酸铁螯合物的环保杀螺剂，其特征在于，所述改性壳聚糖为柠檬酸改性壳聚糖。
  4. 根据权利要求1所述含有磷酸铁螯合物的环保杀螺剂，其特征在于，所述含有磷酸铁螯合物的环保杀螺剂的制备原料还包括润滑剂；所述润滑剂包括硬脂酸镁、十二烷基硫酸钠、植物油和羟基化植物油中的至少一种，优选为羟基化植物油。
  5. 根据权利要求1～4任一项所述含有磷酸铁螯合物的环保杀螺剂，其特征在于，所述磷酸铁螯合物由磷酸铁和螯合剂螯合而成；所述磷酸铁和螯合剂的重量比为1:(0.025～40)。
  6. 根据权利要求5所述含有磷酸铁螯合物的环保杀螺剂，其特征在于，所述磷酸铁和螯合剂的重量比为1:(0.2～5)，优选为1:(0.8～1.2)。
  7. 根据权利要求5所述含有磷酸铁螯合物的环保杀螺剂，其特征在于，所述螯合剂包括谷氨酸二乙酸及其对应的盐、亚氨基二琥珀酸及其对应的盐、二羧甲基丙氨酸及其对应的盐、乙二胺二琥珀酸及其对应的盐以及甲基甘氨酸二乙酸及其对应的盐中的至少一种。
  8. 根据权利要求4所述含有磷酸铁螯合物的环保杀螺剂，其特征在于，所述柠檬酸改性壳聚糖和羟基化植物油的重量比为(0.2～5):1，优选为(0.2～1.5):1。
  9. 一种根据权利要求1～8任一项所述含有磷酸铁螯合物的环保杀螺剂的制备方法，其特征在于，其包括：将含有磷酸铁螯合物的环保杀螺剂的制备原料放入造粒盘造粒，经干燥制得含有磷酸铁螯合物的环保杀螺剂。
  10. 一种根据权利要求1～8任一项所述含有磷酸铁螯合物的环保杀螺剂应用于陆生环境和水生环境中。
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