CN102217595A - Phytocide granule and preparation method of granule - Google Patents
Phytocide granule and preparation method of granule Download PDFInfo
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- CN102217595A CN102217595A CN2011100989138A CN201110098913A CN102217595A CN 102217595 A CN102217595 A CN 102217595A CN 2011100989138 A CN2011100989138 A CN 2011100989138A CN 201110098913 A CN201110098913 A CN 201110098913A CN 102217595 A CN102217595 A CN 102217595A
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- weed killer
- killer herbicide
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Abstract
The invention discloses a phytocide granule and a preparation method of the granule. The preparation method is characterized by including the steps of respectively adding phytocide and bentonite in carboxymethyl chitosan solution, uniformly mixing, dropping the mixed solution in cross-linking agent solution, heating to finish surface cross-linking to obtain solid particles and drying the solid particles to obtain the granular preparation of phytocide. In application, the granule can delay the release of phytocide, reduce drug consumption, prolong action time, improve utilization rate of phytocide and control the pollution of phytocide to the environment.
Description
Technical field:
The present invention relates to a kind of weed killer herbicide granule and preparation method thereof, be meant that specifically a kind of is weed killer herbicide granule of carrier and preparation method thereof with bentonite and CMC.
Background technology:
China's farmland weed face volume is wide, and artificial weeding efficient is low, expense is high, causes chemical weed control technology usable floor area constantly to enlarge.But, existing weed killer herbicide is based on regular dosage forms such as missible oil, after being administered to plant or soil, most of herbicidal activity composition is with the loss of surface runoff or with the soil moisture leaching loss that moves both vertically, enter the face of land or groundwater regime, reduce the weed killer herbicide utilization ratio on the one hand, brought the serious environmental pollution problem on the other hand.Adopt slow release method rationally to regulate the rate of release of herbicidal activity composition, thereby improve drug effect, prolongation lasting period according to the prevention target requirement.Secondly,, can reduce the migration of weed killer herbicide in environment, pollute from source control by control weed killer herbicide burst size.
At present, the slow released herbicide technology can be divided into physical slowly-releasing and chemical type slowly-releasing two big classes.The former mainly relies on the physical bond between carrier and the herbicidal activity composition, and herbicidal activity is not subjected to carriers affect substantially, and slow release formulation processing is relatively easy, development very fast (Wang Baoqing etc., application chemical industry, 2005,34:519 – 523).More microcapsules bag carrier technology and the sorbing material load technology of mainly containing of research in the physical slow release method.In the microcapsules technology, at first former medicine is dispersed into fine droplets, wrap up with macromolecular compounds such as polyurethane, Lauxites then, form and wrap the capsule structure that carries active component in the film, reach the purpose of slowly-releasing during use along with active component through membranous wall to external diffusion.But, thereby microcapsules manufacturing requirements height, complex forming technology, cyst wall easily breaks influences slow release effect.Utilize sorbing material to make preparing carriers slow released herbicide preparation, have the advantage that technology is simple, cost is low.Wherein, clay class rich material resources, cheap, specific surface area is big, and easily modification, and then prepare the modified clay that weed killer herbicide is had good adsorption properties, as herbicide formulations carrier (Y El-Nahhal etc., Pestic Sci, 1999,55:857 – 864).But clay class carrier itself is lower to the load capacity of weed killer herbicide, and the mass content of weed killer herbicide is usually below 4%, and the medicine carrying amount improves the obvious variation of back slow release effect.For this reason, be necessary the novel herbicidal agent formulation of exploitation medicine carrying amount height, had good sustained release effect on the prior art basis.
Summary of the invention:
It is the weed killer herbicide granule of carrier with bentonite and CMC that a first aspect of the present invention purpose is to provide a kind of, use the present invention, can delay the release of weed killer herbicide, reduce formulation rate, prolong action time, improve the weed killer herbicide availability, control the pollution of weed killer herbicide environment.
In order to achieve the above object, the technical scheme taked of the present invention is:
A kind of weed killer herbicide granule is characterized in that: weed killer herbicide, bentonite are added respectively in the carboxymethyl chitosan sugar juice, mix, above-mentioned mixed liquor is splashed in the cross-linking agent solution, heating is finished surface-crosslinked, gets solid particulate matter, and solid particulate matter is drying to obtain the weed killer herbicide granular preparation.
Further limit and be:
Described weed killer herbicide be meant use in the agricultural production to eliminate weeds, protection crops normal growth all kinds of natural or synthesis of chemicals as purpose.
It is the layered clay mineral of main component that described bentonite is meant with the montmorillonite, is included as to improve it to the prepared modified alta-mud of the absorption property of weed killer herbicide.Exchangeable cations is calcium ion or sodium ion between bentonite bed, and modified alta-mud is meant and adopts prior art by resulting product after bentonite and the generation ion-exchange reactions such as metal cation, inorganic acid hydrogen ion, cationic surfactant.
Described CMC is meant on the chitosan molecule structure amino and hydroxyl is replaced the resulting soluble derivative in back by carboxymethyl, and its substitution value can have the preparation method now and obtain between 0.3 ~ 0.99 by buying the market existing procucts or adopting.
Described crosslinking agent is the water soluble salt compounds of multivalent metal cation such as calcium ion, or many aldehyde compounds such as glutaraldehyde, or be the mixing of above-mentioned two kinds of crosslinking agents with certain proportion and form, crosslinking agent of the present invention is that the form with the aqueous solution participates among the preparation method of the present invention.
Of the present invention is the weed killer herbicide granule of carrier with bentonite and CMC, utilizes the water-soluble preparation of CMC can wrap up the mixed liquor of weed killer herbicide; Utilize the quick cross-linking reaction of CMC to prepare the shaping granular preparation; Utilize the parcel of crosslinked carboxymethyl chitosan and the medicine carrying amount that the bentonite suction-operated improves preparation, prolong the release time of weed killer herbicide; Utilize the amido cationic characteristic of CMC, strengthen containing the slow release effect of carboxylic acids weed killer herbicide.
Another aspect of the present invention purpose provides a kind of preparation method of above-mentioned weed killer herbicide granule, may further comprise the steps: preparation CMC content is 0.5% ~ 10%(mass percent, the aqueous solution down together), bentonite and weed killer herbicide are added, mix, wherein the mass ratio of bentonite addition and CMC is 0.2 ~ 5:1, and the mass ratio of weed killer herbicide addition and CMC is 0.1 ~ 2:1.The gained mixed liquor is splashed in the cross-linking agent solution, and heat cross-linking got solid particulate matter after 1 ~ 9 minute, and drying obtains the weed killer herbicide granule.
Beneficial effect of the present invention is: (1) can make extend to more than 300 hours the release time of weed killer herbicide, thereby prolongs the lasting period, has reduced the number of times and the consumption of repetitive administration weed killer herbicide, helps controlling the pesticide pollution problem; (2) granule of moulding be can obtain, facility and safety that weed killer herbicide uses improved; (3) compare with simple alta-mud load, improved the medicine carrying amount of weed killer herbicide, prolonged weed killer herbicide release time.
Description of drawings:
Fig. 1 is the release rate curve map of the weed killer herbicide of the embodiment of the invention 1～3 preparation;
Fig. 2 is the release rate curve map of the weed killer herbicide of comparative example's 1～3 preparation of the present invention.
Embodiment:
Embodiment 1:
5 g CMCs are added in the 100 g water, be stirred to it and dissolve fully, add bentonite 3 g, weed killer herbicide 2 then, 4-D butyl ester (2,4 dichlorophenoxyacetic acid butyl ester) 2 g fully mix and are unit for uniform suspension.The preparation mass concentration is 6% calcium chloride (crosslinking agent) aqueous solution 1000 mL, above-mentioned suspension is added drop-wise in the cross-linking agent solution with peristaltic pump, obtain granular disintegration in reaction under 60 ℃ after 5 minutes, particle is leached, dry 2 h under 70 ℃ obtain the about 0.8 millimeter weed killer herbicide granular preparation of average grain diameter then.Through extraction and analysis, in the preparation 2, the mass content of 4-D butyl ester is 18.2%, 2, and the bag rate of carrying of 4-D butyl ester is 91.0%.
The herbicide formulations of above-mentioned preparation is carried out release experiment, get formulation samples 100 mg and put into 1000 mL water, water sampling analysis weed killer herbicide quality wherein behind the certain hour of interval, calculate the release rate (promptly being discharged into the percentage that weed killer herbicide quality in the water accounts for initial quality in the preparation) of weed killer herbicide under the different time, the results are shown in Figure 1.The weed killer herbicide analytical method can adopt the well-known chromatographic process of analysis of agricultural drugs technical field.
Embodiment 2:
Get bentonite 4.5 g, with 10 mL mass concentrations be that centrifugation went out solids after 20% aqueous sulfuric acid carried out ion-exchange reactions, drying obtains acid activation bentonite 4.0 g.
Above-mentioned acid activation bentonite is added (the CMC mass content is 3%) in the 100 g carboxymethyl chitosan sugar aqueous solutions, after stirring, add weed killer herbicide isopropyl methoxalamine 3 g, fully mix and be unit for uniform suspension.Be added drop-wise to as in the embodiment 1 described cross-linking agent solution with peristaltic pump then, obtain granular disintegration in reaction under 60 ℃ after 3 minutes, then at 70 ℃ of following dry 2 h, obtain the about 0.9 millimeter herbicide formulations of average grain diameter, wherein the isopropyl methoxalamine mass content is 26.5% through extraction and analysis, and the bag rate of carrying of isopropyl methoxalamine is 88.3%.Get said preparation sample 70 mg, adopt embodiment 1 described method to carry out release experiment, obtain the release rate of weed killer herbicide under the different time, the results are shown in Figure 1.
Embodiment 3:
Get bentonite 3 g, with 30 mL mass concentrations be that centrifugation went out solids after 2% hexadecyldimethyl benzyl ammonium aqueous ammonium chloride solution carried out ion-exchange reactions, drying obtains organic modified bentonite 3.1 g.
The preparation mass content is 4% carboxymethyl chitosan sugar aqueous solution 100 g, adds above-mentioned organic modified bentonite and weed killer herbicide alachlor 4 g successively, fully mixes to be unit for uniform suspension.Prepare mass concentration respectively and be calcium chloride water, each 500 mL of glutaraldehyde water solution of 10%, mix the back as crosslinking agent.Above-mentioned suspension is added drop-wise in the cross-linking agent solution with peristaltic pump, obtains granular disintegration in reaction under 50 ℃ after 3 minutes, particle is leached, dry 2 h under 70 ℃ obtain the about 1.0 millimeters weed killer herbicide granular preparation of average grain diameter then.Through extraction and analysis, the mass content of alachlor is 33.8% in the preparation, and the bag rate of carrying of alachlor is 93.9%.Get said preparation sample 55 mg, adopt embodiment 1 described method to carry out release experiment, obtain the release rate of weed killer herbicide under the different time, the results are shown in Figure 1.
The comparative example 1:
Add bentonite 8 g, weed killer herbicide 2 in 100 g water, 4-D butyl ester 2 g fully mix.Because of cross-linking reaction can not take place bentonite,,, obtain the herbicide formulations of powdery then at 70 ℃ of following dry 2 h so this suspension centrifugation is gone out solids.Through extraction and analysis, in the preparation 2, the mass content of 4-D butyl ester is 7.8%, and it is 39.0% that bag carries a rate.Get this powderous preparations 200 mg, adopt embodiment 1 described method to carry out release experiment, obtain the release rate of weed killer herbicide under the different time, the results are shown in Figure 2.
The comparative example 2:
In 100 g water, add acid activation bentonite 7 g, weed killer herbicide isopropyl methoxalamine 3 g, fully mix.The centrifugation of gained suspension is gone out solids,, obtain the herbicide formulations of powdery then at 70 ℃ of following dry 2 h.Through extraction and analysis, the mass content of isopropyl methoxalamine is 10.1% in the preparation, and it is 33.6% that bag carries rate.Get powderous preparations 150 mg, adopt embodiment 1 described method to carry out release experiment, obtain the release rate of weed killer herbicide under the different time, the results are shown in Figure 2.
The comparative example 3:
In 100 g water, add organic modified bentonite 7.1 g, weed killer herbicide alachlor 4 g, fully mix.The centrifugation of gained suspension is gone out solids,, obtain the herbicide formulations of powdery then at 70 ℃ of following dry 2 h.Through extraction and analysis, the mass content of alachlor is 14.9% in the preparation, and it is 41.3% that bag carries rate.Get powderous preparations 100 mg, adopt embodiment 1 described method to carry out release experiment, obtain the release rate of weed killer herbicide under the different time, the results are shown in Figure 2.
Effect comparison:
In conjunction with Fig. 1, Fig. 2 as can be seen, the present invention's employing is the weed killer herbicide granule of carrier with bentonite and CMC; Utilize the parcel of crosslinked carboxymethyl chitosan and the medicine carrying amount that the bentonite suction-operated improves preparation, prolong the release time of weed killer herbicide; Utilize the amido cationic characteristic of CMC, strengthen containing the slow release effect of carboxylic acids weed killer herbicide; Thereby extend to more than 300 hours the release time that can make weed killer herbicide, improved the lasting period, reduced the number of times and the consumption of repetitive administration weed killer herbicide, helps controlling the pesticide pollution problem; And traditional simple alta-mud load, only be about 70 hours its release time, therefore, the present invention has compared with prior art improved the medicine carrying amount of weed killer herbicide, has prolonged weed killer herbicide release time.
Claims (10)
1. weed killer herbicide granule, it is characterized in that: weed killer herbicide, bentonite are added respectively in the carboxymethyl chitosan sugar juice, mix, above-mentioned mixed liquor is splashed in the cross-linking agent solution, heating is finished surface-crosslinked, get solid particulate matter, solid particulate matter is drying to obtain the weed killer herbicide granular preparation.
2. a kind of weed killer herbicide granule according to claim 1 is characterized in that: described bentonite is meant with the montmorillonite to be the layered clay mineral of main component.
3. a kind of weed killer herbicide granule according to claim 2 is characterized in that: exchangeable cations is calcium ion or sodium ion between bentonite bed.
4. a kind of weed killer herbicide granule according to claim 1 is characterized in that: described bentonite is a modified alta-mud.
5. a kind of weed killer herbicide granule according to claim 4 is characterized in that: described modified alta-mud is meant by resulting product after bentonite and metal cation, inorganic acid hydrogen ion or the cationic surfactant generation ion-exchange reactions.
6. a kind of weed killer herbicide granule according to claim 1 is characterized in that: described CMC is meant on the chitosan molecule structure amino and hydroxyl is replaced resulting soluble derivative afterwards by carboxymethyl, and its substitution value is between 0.3 ~ 0.99.
7. a kind of weed killer herbicide granule according to claim 1, it is characterized in that: described crosslinking agent is selected from one or both of multivalent metal cation or many aldehyde compounds.
8. a kind of weed killer herbicide granule according to claim 7 is characterized in that: described multivalent metal cation is the water soluble salt compounds of calcium ion.
9. a kind of weed killer herbicide granule according to claim 7 is characterized in that: described many aldehyde compounds are glutaraldehyde.
10. the preparation method of the weed killer herbicide granule of one of claim 1～9, may further comprise the steps: it is in 0.5% ~ 10% the carboxymethyl chitosan sugar aqueous solution that bentonite, weed killer herbicide are joined mass content, wherein, the mass ratio of bentonite addition and CMC is 0.2 ~ 5:1, the mass ratio of weed killer herbicide addition and CMC is 0.1 ~ 2:1, mix mixed liquor, mixed liquor is splashed in the cross-linking agent solution, heat cross-linking gets solid particulate matter after 1 ~ 9 minute, drying obtains the weed killer herbicide granule.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102578082A (en) * | 2012-01-12 | 2012-07-18 | 中国科学院合肥物质科学研究院 | Method for controlling loss of pesticide at high efficiency and low cost |
| CN102939961A (en) * | 2012-11-06 | 2013-02-27 | 绍兴文理学院 | Pesticide microparticle preparation having core-shell structure and preparation method thereof |
| CN102939960A (en) * | 2012-11-06 | 2013-02-27 | 绍兴文理学院 | Sustained-release herbicide microparticle preparation and preparation method thereof |
| CN103518712A (en) * | 2013-10-30 | 2014-01-22 | 绍兴文理学院 | Sustained-release chloroacetamide herbicide water dispersible granule and preparation method thereof |
| CN106867164A (en) * | 2017-01-20 | 2017-06-20 | 华南理工大学 | A kind of PVA/ starch sustained release films with herbicide controlled release properties and preparation method thereof |
| CN111887244A (en) * | 2020-07-15 | 2020-11-06 | 中国农业科学院植物保护研究所 | Method for preparing prothioconazole sustained-release gel particles by carboxymethyl chitosan-metal ion crosslinking method |
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2011
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Non-Patent Citations (2)
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| 姜曼 等: "纤维素及其复合凝胶对除草剂的控制释放作用", 《现代农药》 * |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102578082A (en) * | 2012-01-12 | 2012-07-18 | 中国科学院合肥物质科学研究院 | Method for controlling loss of pesticide at high efficiency and low cost |
| CN102578082B (en) * | 2012-01-12 | 2014-08-13 | 中国科学院合肥物质科学研究院 | Method for controlling loss of pesticide at high efficiency and low cost |
| CN102939961A (en) * | 2012-11-06 | 2013-02-27 | 绍兴文理学院 | Pesticide microparticle preparation having core-shell structure and preparation method thereof |
| CN102939960A (en) * | 2012-11-06 | 2013-02-27 | 绍兴文理学院 | Sustained-release herbicide microparticle preparation and preparation method thereof |
| CN102939960B (en) * | 2012-11-06 | 2014-07-02 | 绍兴文理学院 | Sustained-release herbicide microparticle preparation and preparation method thereof |
| CN102939961B (en) * | 2012-11-06 | 2014-07-30 | 绍兴文理学院 | Pesticide microparticle preparation having core-shell structure and preparation method thereof |
| CN103518712A (en) * | 2013-10-30 | 2014-01-22 | 绍兴文理学院 | Sustained-release chloroacetamide herbicide water dispersible granule and preparation method thereof |
| CN106867164A (en) * | 2017-01-20 | 2017-06-20 | 华南理工大学 | A kind of PVA/ starch sustained release films with herbicide controlled release properties and preparation method thereof |
| CN106867164B (en) * | 2017-01-20 | 2019-05-14 | 华南理工大学 | A kind of PVA/ starch sustained release film and preparation method thereof with herbicide controlled release properties |
| CN111887244A (en) * | 2020-07-15 | 2020-11-06 | 中国农业科学院植物保护研究所 | Method for preparing prothioconazole sustained-release gel particles by carboxymethyl chitosan-metal ion crosslinking method |
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