CN108849887A - A kind of hydrophilic gel cladded type pesticide product and its preparation method and application - Google Patents
A kind of hydrophilic gel cladded type pesticide product and its preparation method and application Download PDFInfo
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- CN108849887A CN108849887A CN201810521847.2A CN201810521847A CN108849887A CN 108849887 A CN108849887 A CN 108849887A CN 201810521847 A CN201810521847 A CN 201810521847A CN 108849887 A CN108849887 A CN 108849887A
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- pesticide
- hydrophilic gel
- cladded type
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—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 solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G7/00—Botany in general
- A01G7/06—Treatment of growing trees or plants, e.g. for preventing decay of wood, for tingeing flowers or wood, for prolonging the life of plants
-
- 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
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- 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
- A01N37/18—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/26—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Ecology (AREA)
- Forests & Forestry (AREA)
- Botany (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention provides a kind of hydrophilic gel cladded type pesticide products (HGC- pesticide) and its preparation method and application.This method uses starch for substrate, and partially to neutralize acrylates and acrylamide as monomer, with N, pesticide activity component is introduced Raolical polymerizable system by N- methylene-bisacrylamide crosslinking agent in a manner of lotion or aqueous solution.Hydrophilic gel cladded type pesticide product is obtained after reaction product is freeze-dried, and it is introduced into method with the matrix of traditional pesticide and is combined, pesticide soil total residual 10%~40% can be cut down, and the diffusion of pesticide pollution of area source can be controlled to a certain extent while improving pesticide utilization efficiency.
Description
Technical field
The pollution by pesticides abatement that the present invention relates to a kind of based on hydrophilic gel coating technology and control new method, and in particular to
A kind of hydrophilic gel cladded type pesticide product and its preparation method and application.
Background technique
China's grain-production keeps sustainable growth, and pesticide, which is made that, cannot be neglected significant contribution.However, chemical pesticide
Though the raising for being conducive to crop yield largely is excessively used, the intrinsic control action of Agro-ecological System is destroyed, is induced
The drug resistance of harmful organism promotes to increase dosage and forms vicious circle, and then seriously threatens the quality of agricultural products in China
Safety, ecological environment security and human health.In this context, mechanism and regulatory mechanism, Yi Jinong are applied in the control of chemical pesticide decrement
Medicine residual abatement key technology research has become China's agricultural " turn mode, adjust structure ", ensures China's grain security and ecology
One of the grand strategy demand of safety.The key of " pesticide reduction synergy " mainly includes two aspects：First is that high-efficiency low-toxicity environment
The initiative of friendly novel pesticide, second is that the dosage form of existing high-quality pesticide and pesticide application technology are improved.However, opening due to new drug initiative
The hair time is long, costly, and the probability for obtaining the lead compound for meeting various requirement is extremely low.In contrast, for existing excellent
Matter pesticide species carry out physical and chemical performance improvement, develop various new dosage forms and substitution application technique, are playing to greatest extent
While effectiveness, its environment and health risk are reduced, has become the side of giving priority to of domestic and international pesticide developing and application field
One of to.
Gel cladded type pesticide is a kind of compound based on pesticide control-sustained release theory high molecular material-pesticide activity molecule
Object mainly controls pesticide activity molecule in ecological ring by the interaction between high-molecular compound and pesticide activity molecule
Release, Transport And Transformation, residual and biological accumulation in border.The structure basis of gel cladding pesticide is a kind of with superpower hydrophilic energy
The high-molecular gel of power, this kind of macromolecular are presented intercrossed network type 3 D stereo polymer on space structure, on strand
In the presence of a large amount of-NH2, the hydrophilies functional group such as-COOH, Van der Waals force, hydrogen bond, ion can be passed through between pesticide molecule
The generations such as key even covalent bond interaction controls pesticide active ingredient in specific system to specific target, according to pre-
Concentration, time and the space sustained release first set；In addition, according to the molecular characterization of hydrophilic gel cladded type pesticide, gel
A large amount of strongly hydrophilic groups on molecular weight may also be tended to by hydrogen bond, Van der Waals force, covalent bond, ionic bond and molecule
The effects of influence interaction between pesticide activity molecule and surrounding medium, and then influence pesticide activity molecule in ecological environment
In adsorption-desorption, uptake and transport, migration leaching, metabolism/Degradation and Transformation, biological concentration and environment the Behavior laws such as withhold.
Therefore, the preparation of hydrophilic gel cladded type pesticide involved in the present invention can mention to reduce chemical pesticide environmental pollution
For a kind of new approach, there is important scientific value and realistic meaning.
Summary of the invention
The pollution by pesticides abatement that it is an object of the present invention to provide a kind of based on hydrophilic gel coating technology and control new method.
The technical solution adopted by the present invention is that：
The preparation method of hydrophilic gel cladded type pesticide product of the invention includes the following steps：
(1) deionized water is added in N in starch2It is gelatinized under protection, deionized water dosage is 10~30ml/g starch, is obtained
To gelatinized starch；
(2) monomer is added in gelatinized starch, the monomer is acrylates and acrylamide, and the acrylates is
Acrylic acid and sodium hydroxide or potassium hydroxide part neutralized reaction product, acrylates dosage are calculated as starch quality with acrylic acid quality
0.8~1.5 times；Acrylamide monomer dosage is 0.8~1.5 times of starch quality；
(3) crosslinking agent is added, dosage is 3 ‰~the 15 ‰ of monomer molar dosage；Initiator is added, initiator amount is
The 0.5%~2% of monomer molar amount；
(4) pesticide active ingredient is introduced in a manner of lotion or aqueous solution；
(5) by Raolical polymerizable carry out hydrophilic gel cladded type pesticide product preparation, polymerization temperature be 50~
80 DEG C, the reaction time is 1~5h, dry using freeze-drying after reaction.
Preferably, the gelatinization point of the step (1) is 60~90 DEG C, and gelatinization time is 15~75 minutes.
Preferably, in the step (2), the degree of neutralization of acrylates is 50%~90%.
Preferably, crosslinking agent used is N, N- methylene-bisacrylamide in the step (3).
Preferably, initiator used is inorganic peroxy class initiator or redox initiator in the step (3).
Preferably, in the step (4) when introducing pesticide active ingredient using lotion mode, organic phase solvent packet used
Include the one or more of vegetable oil, dimethylbenzene and benzene, cosolvent is one of isopropanol or ethylene glycol ethyl ether or a variety of, used
Surfactant is one of Tw-80, Tw-20 or Triton-X100 or a variety of.
The hydrophilic gel cladded type pesticide product that the method for the invention is prepared is in pollution by pesticides is cut down or controlled
Have application prospect, such as can introduce method (such as pesticide-clay mixture method) agriculture for hydrophilic gel cladded type pesticide product of the invention as matrix
Medicine.
The beneficial effects are mainly reflected as follows：The present invention provides a kind of pesticides based on hydrophilic gel coating technology
Pollution abatement and control new method.This method can promote the abatement of pesticide residue, can disappear while improving pesticide utilization efficiency
Subtract pesticide soil total residual 10%~40%, and controls the diffusion of pesticide pollution of area source to a certain extent.
Detailed description of the invention
Fig. 1 is Graft-starch hydrophilic gel cladded type propyl-ester nitorfen SEM photograph；
Fig. 2 is biological effect of the Graft-starch hydrophilic gel cladded type propyl-ester nitorfen to sensitive plant；
Fig. 3 is the soil mineralization rule of Graft-starch hydrophilic gel cladded type propyl-ester nitorfen；
Fig. 4 is the soil mineralization rule of starch hydrophilic gel cladded type Acetochlor.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This：
Embodiment 1：
Starch 1g is added 20ml deionized water and is gelatinized 30min under the conditions of logical nitrogen at 85 DEG C, is cooled to room temperature, will about
1.07ml acrylic acid is neutralized to 70% with the sodium hydroxide solution of 5mol/L, is added dropwise in gelatinized starch；By about 1.10g propylene
Amide is dissolved into 20% aqueous solution, and will about 0.03g N, N- methylene-bisacrylamide and the dissolution of about 0.13g potassium peroxydisulfate
In wherein, being added dropwise in above-mentioned mixed solution；It then will about 200 μ L dimethylbenzene, about 200 μ L isopropanols, about 100~300 μ L
Tw-80 and 10mg propyl-ester nitorfen active constituent stable emulsion is mixed and made into deionized water, it is molten that above-mentioned mixing is added dropwise
In liquid.It is warming up at 70 DEG C and reacts 3h, after product is freeze-dried, crushes and sieve to obtain Graft-starch hydrophilic gel cladding
Type propyl-ester nitorfen product, stereoscan photograph (SEM) are as shown in Figure 1.It is verified through laboratory test, the gel cladded type propyl ester grass
Ether pesticide product still has obvious phytotoxicity effect to sensitive plant, as a result as shown in Figure 2.
Product uses《OECD chemicals test philosophy》In《304A：The intrinsic biological degradability of soil》With《307：In soil
The conversion of aerobic and anaerobism》The method test.Fig. 3 is the soil mineralization of Graft-starch hydrophilic gel cladded type propyl-ester nitorfen
Rule, the test result display present invention can significantly promote propyl-ester nitorfen at three kinds for the mineralizing and degrading in examination soil, mineralising amount
Relative increase has substantially cut down propyl-ester nitorfen in residual total amount wherein up to 70%~200%.
Embodiment 2：
5g tapioca is placed in 250mL three-necked flask, and 100mL deionized water is added and is gelatinized 30min.It is dropped after the completion of gelatinization
To room temperature.It is neutralized under the NaOH aqueous solution ice-water bath for being 5mol/L with mass fraction by a certain amount of acrylic monomers, degree of neutralization
It is 80%.50mg Acetochlor is dissolved in the NaOH solution of 0.2mol/L, then by a certain amount of acrylamide and N, N- is sub-
Bisacrylamide is dissolved in the aqueous slkali of Acetochlor, and vortex is vibrated to being uniformly mixed, and solution is added dropwise to gelatinization
It is stirred in starch.By a certain amount of K2S2O8It is dissolved in deionized water, is added dropwise in gelatinized starch, warming while stirring
To 70 ± 2 DEG C, insulation reaction 3h, reaction process carries out under nitrogen protection.It is down to room temperature after reaction.Product gel is taken
It is dried after out using vacuum freeze drier, obtains Graft-starch hydrophilic gel cladded type Acetochlor product (HGC-
ACE)。
Product uses《OECD chemicals test philosophy》In《304A：The intrinsic biological degradability of soil》With《307：In soil
The conversion of aerobic and anaerobism》The method test.Fig. 4 is the soil mineralization rule of starch hydrophilic gel cladded type Acetochlor,
The test result display present invention can significantly promote Acetochlor at three kinds for the mineralizing and degrading in examination soil, mineralising amount relative increase
100% is reached as high as, the residual total amount of Acetochlor in the soil has substantially been cut down.
Claims (9)
1. a kind of preparation method of hydrophilic gel cladded type pesticide product (HGC- pesticide), it is characterised in that include the following steps：
(1) deionized water is added in N in starch2It is gelatinized under protection, deionized water dosage is 10~30ml/g starch, is pasted
Change starch；
(2) monomer is added in gelatinized starch, the monomer is acrylates and acrylamide, and the acrylates is propylene
Acid is calculated as the 0.8 of starch quality with sodium hydroxide or potassium hydroxide part neutralized reaction product, acrylates dosage with acrylic acid quality
~1.5 times；Acrylamide monomer dosage is 0.8~1.5 times of starch quality；
(3) crosslinking agent is added, dosage is 3 ‰~the 15 ‰ of monomer molar dosage；Initiator is added, initiator amount is monomer
The 0.5%~2% of mole；
(4) pesticide active ingredient is introduced in a manner of lotion or aqueous solution；
(5) preparation of hydrophilic gel cladded type pesticide product is carried out by Raolical polymerizable, polymerization temperature is 50~80 DEG C,
Reaction time is 1~5h, dry using freeze-drying after reaction.
2. the preparation method of hydrophilic gel cladded type pesticide product according to claim 1, it is characterised in that the step
Suddenly the gelatinization point of (1) is 60~90 DEG C, and gelatinization time is 15~75 minutes.
3. the preparation method of hydrophilic gel cladded type pesticide product according to claim 1, it is characterised in that the step
(2) in, the degree of neutralization of acrylates is 50%~90%.
4. the preparation method of hydrophilic gel cladded type pesticide product according to claim 1, it is characterised in that the step
(3) crosslinking agent used is N,N methylene bis acrylamide in.
5. the preparation method of hydrophilic gel cladded type pesticide product according to claim 1, it is characterised in that the step
(3) initiator used is inorganic peroxy class initiator or redox initiator in.
6. the preparation method of hydrophilic gel cladded type pesticide product according to claim 1, it is characterised in that the step
(4) in when introducing pesticide active ingredient using lotion mode, organic phase solvent used includes the one of vegetable oil, dimethylbenzene and benzene
Kind is a variety of, and cosolvent is one of isopropanol or ethylene glycol ethyl ether or a variety of, and surfactant used is Tw-80, Tw-20
Or one of Triton-X100 or a variety of.
7. a kind of hydrophilic gel cladded type pesticide product that any one of -6 methods are prepared according to claim 1.
8. application of the hydrophilic gel cladded type pesticide product described in claim 7 in pollution by pesticides is cut down or controlled.
9. application according to claim 8, it is characterised in that introduced hydrophilic gel cladded type pesticide product as matrix
Method pesticide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810521847.2A CN108849887A (en) | 2018-05-28 | 2018-05-28 | A kind of hydrophilic gel cladded type pesticide product and its preparation method and application |
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| CN201810521847.2A CN108849887A (en) | 2018-05-28 | 2018-05-28 | A kind of hydrophilic gel cladded type pesticide product and its preparation method and application |
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| CN108849887A true CN108849887A (en) | 2018-11-23 |
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| CN201810521847.2A Pending CN108849887A (en) | 2018-05-28 | 2018-05-28 | A kind of hydrophilic gel cladded type pesticide product and its preparation method and application |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016113666A1 (en) * | 2015-01-13 | 2016-07-21 | Agresearch Limited | Agricultural composition |
| CN106259320A (en) * | 2016-07-21 | 2017-01-04 | 河南师范大学 | A kind of water-absorbing-retaining sustained-release pesticides and preparation method thereof |
-
2018
- 2018-05-28 CN CN201810521847.2A patent/CN108849887A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016113666A1 (en) * | 2015-01-13 | 2016-07-21 | Agresearch Limited | Agricultural composition |
| CN106259320A (en) * | 2016-07-21 | 2017-01-04 | 河南师范大学 | A kind of water-absorbing-retaining sustained-release pesticides and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张素芬: ""亲水凝胶包覆型丙酯草醚的制备、性能及其土壤行为规律的示踪法研究"", 《中国博士学位论文全文数据库》 * |
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