CN101785453B - Photocrosslinkable controlled-release long-acting pesticide preparation, preparation method and application thereof - Google Patents
Photocrosslinkable controlled-release long-acting pesticide preparation, preparation method and application thereof Download PDFInfo
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- CN101785453B CN101785453B CN2010101254083A CN201010125408A CN101785453B CN 101785453 B CN101785453 B CN 101785453B CN 2010101254083 A CN2010101254083 A CN 2010101254083A CN 201010125408 A CN201010125408 A CN 201010125408A CN 101785453 B CN101785453 B CN 101785453B
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Abstract
The invention relates to a photocrosslinkable controlled-release long-acting pesticide preparation, the controlled-release active component of which is photocrosslinkable carboxymethyl chitosan produced by the reaction between carboxymethyl chitosan and photocrosslinking agent 4-azidobenzaldehyde, and the preparation is prepared by the following method: the aqueous solution of carboxymethyl chitosan is taken, the organic solution of 4-azidobenzaldehyde is added according to the molar ratio (1:(0.01 to 10)) of the carbohydrate unit of carboxymethyl chitosan to 4-azidobenzaldehyde, uniform mixing is carried out under the temperature of 0 DEG C to 30 DEG C in the dark, and thereby photocrosslinkable carboxymethyl chitosan mixture is obtained; and the mixture is then added in pesticide, and is uniformly mixed in the dark. The preparation is sprayed or sprinkled on the surfaces of agricultural and forest plants, and can quickly respond to the solar ultraviolet light to initiate azido photocrosslinking to form pesticide membranes stuck on the surfaces or injured parts of plants, and thereby the quick loss of a great deal of pesticide can be avoided. The preparation method is simple, can be easily operated, and is suitable for industrialized production.
Description
Technical field
The present invention relates to pesticide field, particularly a kind of controlled release agricultural chemicals durative action preparation of Photocrosslinkable.
Background technology
The sick worm harm of agriculture and forestry plant often causes heavy economic losses to agriculture and forestry.In order to control or to alleviate this harm, people usually need spray various agricultural chemicals to various agriculture and forestry plants.Yet but there is following deficiency in existing agricultural chemicals:
(1) the sick worm harm phase of agriculture and forestry plant and the lasting period of existing agricultural chemicals do not match, because the growth cycle of agriculture and forestry plant is longer, and all can receive the harm of disease worm different vegetative period, thereby have the long sick worm harm phase; The lasting period of existing agricultural chemicals is long then more than 10 day, and is short then have only several days, thereby in the harm phase, must repeatedly use agricultural chemicals, often needs use once in one day sometimes, just can reach the purpose that control endangers.
(2) existing many agricultural chemicals have inevitably caused the severe contamination of environment (comprising air, water quality and soil); Owing to agricultural chemicals in reasons such as the poor adhesive force of plant surface and rain drop erosiones; Cause a large amount of losses (turnover rate is up to 60～90%, have only 30～10% be used effectively) of agricultural chemicals.The agricultural chemicals that runs off gets into the animals and plants food chain through the environment that pollutes such as water body etc., causes health and ecological serious threat.
(3) heavy dose of agricultural chemicals also can cause the disease worm to produce drug resistance with frequent use, has increased the weight of the using dosage and the number of times of agricultural chemicals.
In order to address the above problem, people will delay controlled-release technology exactly and apply in the agricultural chemicals dispose procedure except competitively developing low toxicity or nontoxic ecological agricultural chemical, develop the Multiple Pesticides sustained-release preparation, like microcapsule formulations, granule and nano pesticide etc.These preparations are relatively poor at the adhesive force of plant surface mostly, are unfavorable for medicine on agriculture and forestry plant surface or endangered the long-acting release at position, and there is complex manufacturing technology in these preparation majorities in addition, the defective that cost is higher.Chinese invention patent CN1561718A once disclosed a kind of pesticide slow-releasing agent; Said preparation has that preparation technology is simple, cost is low, can improve advantages such as agricultural chemicals availability; But owing to adopted not biodegradable polyvinyl alcohol as carrier material, long-term use can't fundamentally solve problem of environmental pollution; In addition, said preparation does not have controlled release properties yet.
CMC is the derivative of shitosan, is a kind of polyampholyte, has water-soluble, excellent biological compatibility and biodegradable, is widely used in the medical carrier aspect.CMC can form semipermeable membrane fruit and vegetable or plant surface, and this film has permselectivity to gas, can regulate the physiological metabolism of fruits and vegetables or plant, is desirable coating antistaling agent; In addition; CMC has also that the moisture absorption is preserved moisture, antibacterial, premium properties such as tack is strong; The carboxyl of introducing in the molecule also provides the environmental sensitivity functional group improving the water miscible while of shitosan, makes CMC become the excellent materials of preparation pH susceptibility gel mould.In view of the plurality of advantages of CMC, use it for the controlled release carrier of agricultural chemicals, should have good potentiality.
Summary of the invention
Technical problem to be solved by this invention is: in order to solve the problem that exists in the prior art, a kind of controlled release agricultural chemicals durative action preparation of novel environment sensitive is provided, this method not only technology is simple; Operation easily; And the preparation of preparation is surperficial in agriculture and forestry plant through spraying or spray function, can respond the crosslinked patent medicine film of sunshine fast, and then adheres to its surface or endangered the position; Wait pH to stimulate through airborne tide dew the swelling response takes place, and then discharge agricultural chemicals.
The present invention solves its technical problem and adopts following technical scheme:
The controlled release agricultural chemicals durative action preparation of Photocrosslinkable provided by the invention; Its effective ingredient is the CMC of the Photocrosslinkable of CMC and the generation of photocrosslinking agent 4-phenylazide formolite reaction; Said preparation is processed by following method: the aqueous solution of getting CMC; According to the sugar unit of CMC and the mol ratio of 4-phenylazide formaldehyde is 1: (0.01～10) adds the organic solution of 4-phenylazide formaldehyde; Mix in 0～30 ℃ of lucifuge, obtain the CMC mixed solution of Photocrosslinkable; Then, this mixed solution is added in the agricultural chemicals, obtain the controlled release agricultural chemicals durative action preparation of said Photocrosslinkable after lucifuge mixes; Said agricultural chemicals is a kind of in insecticide, bactericide, weed killer herbicide or the plant growth regulator, or several kinds of mixtures.
The organic solution of said 4-phenylazide formaldehyde can be the solution of ethanol, acetone or dimethyl formamide one-component solvent.
The organic solution of said 4-phenylazide formaldehyde can be the mixed solution of the multicomponent solvent of ethanol and acetone composition, and the two weight proportion is an arbitrary proportion.
The organic solution of said 4-phenylazide formaldehyde can be the mixed solution of the multicomponent solvent of ethanol and dimethyl formamide composition, and the two weight proportion is an arbitrary proportion.
The present invention adopts following method to prepare the controlled release agricultural chemicals durative action preparation of Photocrosslinkable, and its step comprises:
(1) preparation of carboxymethyl chitosan sugar aqueous solution: with degree of substitution by carboxymethyl is that 0.1～1.8 CMC is added to the water, and the mass concentration of CMC is 0.5～10%, under room temperature, stirs then;
(2) preparation of photocrosslinking agent 4-phenylazide formalin: 4-phenylazide formaldehyde is dissolved in organic solvent, obtains the organic solution of 4-phenylazide formaldehyde, the weight percent concentration of the organic solution of 4-phenylazide formaldehyde is 5%～85%;
(3) preparation of the CMC mixed solution of Photocrosslinkable: the aqueous solution of getting CMC; According to the sugar unit of CMC and the mol ratio of 4-phenylazide formaldehyde is 1: (0.01～10) adds the organic solution of 4-phenylazide formaldehyde; Mix in 0～30 ℃ of lucifuge, obtain the CMC mixed solution of Photocrosslinkable;
(4) preparation of the controlled release agricultural chemicals durative action preparation of Photocrosslinkable: agricultural chemicals is added in the CMC mixed solution, mix the controlled release agricultural chemicals durative action preparation that obtains said Photocrosslinkable.
Described CMC mixed solution can be in any form, in any ratio and insecticide, bactericide, weed killer herbicide, the plant growth regulator one or more mix directly and use, or after hybrid process, use.Described any form is included as emulsifier, solubilizer or the surfactant that improves the water-soluble or dispersed of water-insoluble agricultural chemicals and add.
The controlled release agricultural chemicals durative action preparation of the Photocrosslinkable of the present invention's preparation; It is surperficial in agriculture and forestry plant through spraying or spray function; Under the effect of radiant light, be cross-linked into the surface that can stick to agriculture and forestry plant or endangered the medicine film at position; The stimulation generation swelling response that this medicine film reveals through airborne tide, and then discharge agricultural chemicals.
The controlled release agricultural chemicals durative action preparation of the Photocrosslinkable of the present invention's preparation; It is surperficial in agriculture and forestry plant through spraying or spray function; Under the effect of sunshine or artificial ultraviolet light, be cross-linked into the surface that can stick to agriculture and forestry plant or endangered the medicine film at position; The stimulation generation swelling response that this medicine film reveals through airborne tide, and then discharge agricultural chemicals.
That the present invention adopts is nontoxic, can give birth to degraded and water-soluble good CMC and the CMC of photocrosslinking agent 4-phenylazide formaldehyde at room temperature or the generation of reaction below room temperature Photocrosslinkable; Mix or be processed to form the sustained-release pesticides durative action preparation of Photocrosslinkable then with agricultural chemicals and water, compared with prior art have following major advantage:
(1) this preparation is surperficial in agriculture and forestry plant through spraying or spray function, can respond the ultraviolet light cross-linking patent medicine film of the sun fast, and adheres to its surface or endangered the position, thereby can avoid quick and a large amount of losses of agricultural chemicals.
(2) this preparation has the susceptibility of pH at the surperficial medicine film that forms of agriculture and forestry plant, and it can respond airborne tide and reveal stimulation generation swellings such as pH (≈ 5.6), and then discharges agricultural chemicals.
(3) this preparation is a semipermeable membrane at the medicine film that the agriculture and forestry plant surface forms, and this film has permselectivity to gas, can regulate the physiological metabolism of plant, has guaranteed the mass exchange of agriculture and forestry plant and environment.
(4) this preparation is the very thin very thin clear gel film of one deck at the medicine film that the agriculture and forestry plant surface forms, and can guarantee the energy exchange (being photosynthesis) of agriculture and forestry plant and environment.
(5) this preparation process thereof is simple, and operation is suitable for suitability for industrialized production easily.
Description of drawings
Fig. 1 and Fig. 2 are the sunshine cross-linked gel medicine film sem photograph of the present invention's preparation.
Fig. 3 is the responsive swelling curve figure of the pH of the sunshine cross-linked gel film of the present invention's preparation.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described further, but not only is confined to following embodiment.
Embodiment 1:
With degree of substitution by carboxymethyl be 0.8 carboxymethyl chitosan sugar aqueous solution and photocrosslinking agent 4-phenylazide formaldehyde ethanolic solution according to mol ratio (mol ratio of the sugar unit of CMC and 4-phenylazide formaldehyde) be 1: 1.2 under room temperature lucifuge mix, obtain the CMC mixed solution of Photocrosslinkable.Valid density according to the CMC of the effective dose of bactericide and Photocrosslinkable during use adds the water preparation, and spraying is used.
Embodiment 2:
With degree of substitution by carboxymethyl be 1.0 carboxymethyl chitosan sugar aqueous solutions and photocrosslinking agent 4-phenylazide formaldehyde ethanol according to mol ratio (mol ratio of the sugar unit of CMC and 4-phenylazide formaldehyde) be 1: 1.0 under room temperature lucifuge mix, obtain the CMC mixed solution of Photocrosslinkable.Valid density according to the CMC of the effective dose of insecticide and Photocrosslinkable during use adds the water preparation, and spraying is used.
Embodiment 3:
With degree of substitution by carboxymethyl be 1.2 carboxymethyl chitosan sugar aqueous solutions and photocrosslinking agent 4-phenylazide formaldehyde ethanol according to mol ratio (mol ratio of the sugar unit of CMC and 4-phenylazide formaldehyde) be 1: 0.8 under room temperature lucifuge mix, obtain the CMC mixed solution of Photocrosslinkable.Valid density according to the CMC of the effective dose of weed killer herbicide and Photocrosslinkable during use adds the water preparation, and spraying is used.
Embodiment 4: be the N of 1.0 carboxymethyl chitosan sugar aqueous solutions and photocrosslinking agent 4-phenylazide formaldehyde with degree of substitution by carboxymethyl; N-dimethyl formyl solution is to mix at 1: 0.05 according to mol ratio (mol ratio of the sugar unit of CMC and 4-phenylazide formaldehyde), obtains the CMC mixed solution of Photocrosslinkable.Valid density according to the CMC of the effective dose of plant growth regulator and Photocrosslinkable during use adds the water preparation, and spraying is used.
Embodiment 5: be the ethanol of 1.0 carboxymethyl chitosan sugar aqueous solutions and photocrosslinking agent 4-phenylazide formaldehyde with degree of substitution by carboxymethyl: the mixed solution of acetone (volume ratio 1: 1) is to mix at 1: 0.8 according to mol ratio (mol ratio of the sugar unit of CMC and 4-phenylazide formaldehyde), obtains the CMC mixed solution of Photocrosslinkable.Valid density according to the CMC of acaricidal effective dose and Photocrosslinkable during use adds the water preparation, and spraying is used.
The Photocrosslinkable carboxymethyl chitosan sugar juice of preparation in the foregoing description 1,2,3,4,5 is smeared on glass plate, be positioned over radiation formation cross-linked gel film under the sunshine.Fig. 1 and Fig. 2 are photo-crosslinking gel medicine film sem photograph among the embodiment 1～4.Measure the swelling ratio of gel in different pH buffer with weight method, to investigate the pH susceptibility of hydrogel.Specific as follows:
Be cut into the disk that diameter is 1cm to pH sensitive aqueous gel synthetic in the foregoing description; Put into a series of pH value (2.2,3.0,4.0,5.0,6.0,7.0,8.0) buffer solution respectively; Take out at a distance from a period of time; Weigh after drying hydrogel surface moisture with filter paper, till the weight that proceeds to continuous three swelling behaviors of weighing no longer changes.Be calculated as follows its equilibrium swelling rate: SR=100 (W-W0)/W0 wherein, the gross weight of hydrogel when W is swelling equilibrium, W0 is the weight of xerogel.With SR the pH value is mapped then, promptly get the pH swelling curve figure of sunshine cross-linked gel film shown in Figure 1.
The pH swelling equilibrium curve that has shown gel mould among the embodiment 1～4 among Fig. 3 respectively; The result shows that the crosslinked gel mould of sunshine has pH susceptibility preferably, and its equilibrium swelling rate changes with the variation of pH value; When pH≤4, the equilibrium swelling rate of gel mould is all very low; When pH>=5, the equilibrium swelling rate of gel mould significantly increases, and subtracts gradually down along with the increase of the reduction of degree of substitution by carboxymethyl and photocrosslinking agent mol ratio.Because the pH of morning dew is greatly about about 5.6, so this result shows that swelling takes place the pH that the gel mould that wrap up agricultural chemicals can respond morning dew, thereby on the agriculture and forestry plant surface or the position generation drug of being injured; In addition,, can regulate and control the swelling rate of gel mould, thereby the diffusion and the rate of release of regulating medicine in the film realize that controlled delivery of pharmaceutical agents discharges through the substitution value of adjusting CMC carboxymethyl and the concentration of photocrosslinking agent.
Claims (8)
1. the controlled release agricultural chemicals durative action preparation of a Photocrosslinkable; It is characterized in that said preparation controlled release effective ingredient is the CMC of the Photocrosslinkable of CMC and the generation of photocrosslinking agent 4-phenylazide formolite reaction; Said preparation is processed by following method: the aqueous solution of getting CMC; According to the sugar unit of CMC and the mol ratio of 4-phenylazide formaldehyde is 1: (0.01～10) adds the organic solution of 4-phenylazide formaldehyde; Mix in 0～30 ℃ of lucifuge, obtain the CMC mixed solution of Photocrosslinkable; Then, this mixed solution is added in the agricultural chemicals, obtain the controlled release agricultural chemicals durative action preparation of said Photocrosslinkable after lucifuge mixes; Said agricultural chemicals is a kind of in insecticide, bactericide, weed killer herbicide or the plant growth regulator, or several kinds of mixtures.
2. the controlled release agricultural chemicals durative action preparation of Photocrosslinkable according to claim 1, the organic solution that it is characterized in that said 4-phenylazide formaldehyde is the solution of ethanol, acetone or dimethyl formamide one-component solvent.
3. the controlled release agricultural chemicals durative action preparation of Photocrosslinkable according to claim 1, the organic solution that it is characterized in that said 4-phenylazide formaldehyde are the mixed solutions of the multicomponent solvent formed of ethanol and acetone, and the two weight proportion is an arbitrary proportion.
4. the controlled release agricultural chemicals durative action preparation of Photocrosslinkable according to claim 1, the organic solution that it is characterized in that said 4-phenylazide formaldehyde are the mixed solutions of the multicomponent solvent formed of ethanol and dimethyl formamide, and the two weight proportion is an arbitrary proportion.
5. the preparation method of the controlled release agricultural chemicals durative action preparation of a Photocrosslinkable is characterized in that adopting following method to prepare the controlled release agricultural chemicals durative action preparation of Photocrosslinkable, and its step comprises:
(1) preparation of carboxymethyl chitosan sugar aqueous solution: with degree of substitution by carboxymethyl is that 0.1～1.8 CMC is added to the water, and the mass concentration of CMC is 0.5～10%, under room temperature, stirs then;
(2) preparation of photocrosslinking agent 4-phenylazide formalin: 4-phenylazide formaldehyde is dissolved in organic solvent, obtains the organic solution of 4-phenylazide formaldehyde, the weight percent concentration of the organic solution of 4-phenylazide formaldehyde is 5%～85%;
(3) preparation of the CMC mixed solution of Photocrosslinkable: the aqueous solution of getting CMC; According to the sugar unit of CMC and the mol ratio of 4-phenylazide formaldehyde is 1: (0.01～10) adds the organic solution of 4-phenylazide formaldehyde; Mix in 0～30 ℃ of lucifuge, obtain the CMC mixed solution of Photocrosslinkable; Said CMC mixed solution is used in any form, any ratio and agricultural chemicals are insecticide, bactericide, weed killer herbicide, plant growth regulator one or more mix directly and use, or after hybrid process, use; Described any form is included as emulsifier, solubilizer or the surfactant that improves the water-soluble or dispersed of water-insoluble agricultural chemicals and add;
(4) preparation of the controlled release agricultural chemicals durative action preparation of Photocrosslinkable: agricultural chemicals is added in the CMC mixed solution, mix the controlled release agricultural chemicals durative action preparation that obtains said Photocrosslinkable.
6. the purposes of the controlled release agricultural chemicals durative action preparation of the Photocrosslinkable of the said method of claim 5 preparation; It is characterized in that: said preparation is surperficial in agriculture and forestry plant through spraying or spray function; Under the effect of radiant light, be cross-linked into the surface that can stick to agriculture and forestry plant or endangered the medicine film at position; The stimulation generation swelling response that this medicine film reveals through airborne tide, and then discharge agricultural chemicals.
7. purposes according to claim 6 is characterized in that described radiant light is a sunshine, or artificial ultraviolet light.
8. purposes according to claim 6; It is characterized in that said preparation passes through spraying or spray function is surperficial in agriculture and forestry plant; Under the effect of sunshine or artificial ultraviolet light, be cross-linked into the surface that can stick to agriculture and forestry plant or endangered the medicine film at position; The stimulation generation swelling response that this medicine film reveals through airborne tide, and then discharge agricultural chemicals.
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| CN2010101254083A CN101785453B (en) | 2010-03-11 | 2010-03-11 | Photocrosslinkable controlled-release long-acting pesticide preparation, preparation method and application thereof |
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| CN101785453B true CN101785453B (en) | 2012-07-18 |
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| CN106719630A (en) * | 2016-11-16 | 2017-05-31 | 武汉理工大学 | Optical Response controlled release nanometer pesticidal preparations and its preparation method and application |
| CN110140717A (en) * | 2019-05-31 | 2019-08-20 | 贵州省生物研究所 | A kind of photoresponse controlled release pesticide film and its preparation method and application |
| CN111602532A (en) * | 2020-05-19 | 2020-09-01 | 浙江工业大学 | Method for improving pesticide use efficiency by using carbon nano tube |
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| CN101366972A (en) * | 2008-09-28 | 2009-02-18 | 浙江大学 | Preparation method for three-dimensional ordered stephanoporate chitosan bone renovating bracket material |
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| US7985601B2 (en) * | 2002-03-08 | 2011-07-26 | The Regents Of The University Of California | Tunable, semi-interpenetrating polymer networks (sIPNS) for medicine and biotechnology |
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| CN101366972A (en) * | 2008-09-28 | 2009-02-18 | 浙江大学 | Preparation method for three-dimensional ordered stephanoporate chitosan bone renovating bracket material |
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