阅读说明：本技术 含吡唑醚菌酯和氟环唑的水悬浮剂及其制备方法 (Water suspending agent containing pyraclostrobin and epoxiconazole and preparation method thereof ) 是由 吴丽文 张小敏 谭葵 廖联安 于 2021-08-09 设计创作，主要内容包括：本申请提供一种含吡唑醚菌酯和氟环唑的水悬浮剂及其制备方法。上述含吡唑醚菌酯和氟环唑的水悬浮剂的组分包括如下质量份的各组分：吡唑醚菌酯10份～25份、氟环唑5份～15份、EO-PO嵌段共聚物润湿剂1份～4份、羧酸盐类分散剂6份～12份、增稠剂1.4份～3.2份及去离子水35份～72份。上述含吡唑醚菌酯和氟环唑的水悬浮剂的分散性较好、贮存稳定性较好、药效高且持效期长。(The application provides an aqueous suspending agent containing pyraclostrobin and epoxiconazole and a preparation method thereof. The water suspending agent containing the pyraclostrobin and the epoxiconazole comprises the following components in parts by mass: 10-25 parts of pyraclostrobin, 5-15 parts of epoxiconazole, 1-4 parts of EO-PO block copolymer wetting agent, 6-12 parts of carboxylate dispersant, 1.4-3.2 parts of thickening agent and 35-72 parts of deionized water. The water suspending agent containing pyraclostrobin and epoxiconazole has the advantages of good dispersibility, good storage stability, high drug effect and long lasting period.)

1. The water suspending agent containing pyraclostrobin and epoxiconazole is characterized by comprising the following components in parts by mass:

2. the aqueous suspension concentrate containing pyraclostrobin and epoxiconazole according to claim 1, wherein the thickening agent comprises xanthan gum, magnesium aluminum silicate and white carbon black.

3. The water suspending agent containing pyraclostrobin and epoxiconazole according to claim 2, wherein the mass ratio of the xanthan gum to the magnesium aluminum silicate to the white carbon black is (0.1-0.2): (0.3-1): (1-2).

4. The water suspending agent containing pyraclostrobin and epoxiconazole according to claim 1, which is characterized by further comprising the following components in parts by mass:

3-5 parts of an antifreezing agent.

5. The water suspension concentrate containing pyraclostrobin and epoxiconazole according to claim 4, wherein the antifreezing agent is at least one of ethylene glycol, propylene glycol and polyethylene glycol.

6. The water suspending agent containing pyraclostrobin and epoxiconazole according to claim 1, which is characterized by further comprising the following components in parts by mass:

0.1 to 0.5 portion of defoaming agent.

7. The water suspending agent containing pyraclostrobin and epoxiconazole according to claim 1, which is characterized by further comprising the following components in parts by mass:

0.1 to 0.5 portion of preservative.

8. A preparation method of an aqueous suspending agent containing pyraclostrobin and epoxiconazole is characterized by comprising the following steps:

mixing an EO-PO block copolymer wetting agent, a carboxylate dispersant, a thickening agent, an antifreezing agent and a first preset amount of deionized water, and stirring for the first time to obtain a first mixture;

adding pyraclostrobin and epoxiconazole into the first mixture to obtain a second mixture;

grinding the second mixture to obtain a third mixture;

mixing xanthan gum, a defoaming agent, a preservative and a second preset amount of deionized water to obtain a fourth mixture;

and adding the fourth mixture into the third mixture, and carrying out second stirring operation to obtain the water suspending agent containing pyraclostrobin and epoxiconazole.

9. The method for preparing the pyraclostrobin-containing aqueous suspension concentrate as claimed in claim 8, wherein the method for preparing the pyraclostrobin-containing aqueous suspension concentrate as claimed in claim 8 further comprises the steps of, after the step of adding pyraclostrobin and epoxiconazole to the first mixture to obtain the second mixture and before the step of subjecting the second mixture to a grinding operation to obtain the third mixture:

and carrying out first homogeneous dispersion operation on the second mixture.

10. The method for preparing the water suspending agent containing the pyraclostrobin and the epoxiconazole according to the claim 8, characterized in that after the step of mixing xanthan gum, an antifoaming agent, a preservative and a second preset amount of the deionized water and performing a second stirring operation to obtain a fourth mixture, and before the step of adding the fourth mixture into the third mixture and performing the second stirring operation to obtain the water suspending agent containing the pyraclostrobin and the epoxiconazole, the method for preparing the water suspending agent containing the pyraclostrobin and the epoxiconazole further comprises the following steps:

and carrying out second homogeneous dispersion operation on the fourth mixture.

Technical Field

The invention relates to the field of pesticides, and particularly relates to a water suspending agent containing pyraclostrobin and epoxiconazole and a preparation method thereof.

Background

Pyraclostrobin is a strobilurin fungicide with pyrazole structure developed in 1993 by basf, germany. Pyraclostrobin is unique in action mechanism, is a mitochondrial respiration inhibitor, inhibits mitochondrial respiration by preventing electron transfer between cytochrome b and c1, and enables mitochondria to produce and provide energy (ATP) required by normal metabolism of cells, and finally leads to cell death.

Indoor and field experiments show that pyraclostrobin can prevent and treat county diseases caused by germs of Ascomycetes, Basidiomycetes, Deuteromycetes, oomycetes and the like. It has strong inhibiting effect on spore germination and growth of leaf mycelium, and has protective and therapeutic activity. It also has permeability and local systemic activity, long effective period and rain wash resistance. The agent is widely used for controlling diseases of wheat, rice, peanuts, grapes, vegetables, potatoes, bananas, lemons, coffee, fruit trees, walnuts, tea trees, tobacco and ornamental plants, lawns and other field crops. Pyraclostrobin is not only low in toxicity and safe for non-target organisms, but also safe and friendly for both users and the environment, and has been listed as a "risk-reducing candidate agent" by the U.S. EPA.

Epoxiconazole is a systemic triazole fungicide, can inhibit the synthesis of ergosterol of pathogenic bacteria and inhibit the formation of cell walls of the pathogenic bacteria, has strong affinity to a fungal enzyme (C14 demethylase) and can inhibit pathogenic fungi more effectively compared with the existing fungicides. Epoxiconazole can increase the chitinase activity of crops, cause contraction of fungal haustorium and inhibit pathogen invasion, which is a unique characteristic of epoxiconazole in all triazole products. The pesticide composition has good control effect on leaf spot, powdery mildew and rust disease on crops such as bananas, scallion, garlic, celery, beans, melons, asparagus, peanuts, beet and the like, and diseases such as anthracnose, white rot disease and the like on grapes. The research of the mixed pesticide can not only enlarge the application range of the pesticide and reduce the probability of drug resistance, but also reduce the agricultural cost and improve the effect of the pesticide.

However, the suspending agent of pyraclostrobin and epoxiconazole has the problem of easy layering and crystallization during storage, and is very easy to cause austenite ripening and rapid in particle size growth after being placed at normal temperature during or after thermal storage. In particular to the problems that the suspending agent of pyraclostrobin and epoxiconazole is easy to generate heat in the preparation and grinding process to cause the melting of raw pesticide, and the slurry is recrystallized after being recovered to normal temperature.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides the water suspending agent containing the pyraclostrobin and the epoxiconazole, which has the advantages of good dispersibility, good storage stability, high drug effect and long lasting period, and the preparation method thereof.

The purpose of the invention is realized by the following technical scheme:

an aqueous suspending agent containing pyraclostrobin and epoxiconazole comprises the following components in parts by mass:

in one embodiment, the thickener comprises xanthan gum, magnesium aluminum silicate and white carbon black.

In one embodiment, the mass ratio of the xanthan gum to the magnesium aluminum silicate to the white carbon black is (0.1-0.2): (0.3-1): (1-2).

In one embodiment, the water suspending agent containing pyraclostrobin and epoxiconazole further comprises the following components in parts by mass:

3-5 parts of an antifreezing agent.

In one embodiment, the antifreeze agent is at least one of ethylene glycol, propylene glycol, and polyethylene glycol.

In one embodiment, the water suspending agent containing pyraclostrobin and epoxiconazole further comprises the following components in parts by mass:

0.1 to 0.5 portion of defoaming agent.

In one embodiment, the water suspending agent containing pyraclostrobin and epoxiconazole further comprises the following components in parts by mass:

0.1 to 0.5 portion of preservative.

A preparation method of an aqueous suspending agent containing pyraclostrobin and epoxiconazole comprises the following steps:

mixing an EO-PO block copolymer wetting agent, a carboxylate dispersant, a thickening agent, an antifreezing agent and a first preset amount of deionized water, and stirring for the first time to obtain a first mixture;

adding pyraclostrobin and epoxiconazole into the first mixture to obtain a second mixture;

grinding the second mixture to obtain a third mixture;

mixing xanthan gum, a defoaming agent, a preservative and a second preset amount of deionized water to obtain a fourth mixture;

and adding the fourth mixture into the third mixture, and carrying out second stirring operation to obtain the water suspending agent containing pyraclostrobin and epoxiconazole.

In one embodiment, the preparation method of the water suspension containing pyraclostrobin and epoxiconazole further comprises the following steps after the step of adding pyraclostrobin and epoxiconazole to the first mixture to obtain a second mixture and before the step of grinding the second mixture to obtain a third mixture:

and carrying out first homogeneous dispersion operation on the second mixture.

In one embodiment, after the step of mixing xanthan gum, an antifoaming agent, a preservative and a second preset amount of deionized water and performing a second stirring operation to obtain a fourth mixture, and before the step of adding the fourth mixture into the third mixture and performing the second stirring operation to obtain the water suspending agent containing pyraclostrobin and epoxiconazole, the preparation method of the water suspending agent containing pyraclostrobin and epoxiconazole further comprises the following steps:

and carrying out second homogeneous dispersion operation on the fourth mixture.

Compared with the prior art, the invention has at least the following advantages:

1. the water suspending agent containing the pyraclostrobin and the epoxiconazole is prepared by compounding the pyraclostrobin and the epoxiconazole, so that the water suspending agent has the advantages of high internal absorption speed, high drug effect and long lasting period. The carboxylate dispersant is adopted as the dispersant in the water suspending agent containing the pyraclostrobin and the epoxiconazole, the comb-shaped structure of the carboxylate is favorable for the spatial repulsion between particles in the water suspending agent containing the pyraclostrobin and the epoxiconazole, so that the water suspending agent containing the pyraclostrobin and the epoxiconazole can generate better steric hindrance effect, and prevent the particles from being collided during Brownian motion to cause flocculation and agglomeration of the particles in a dispersed phase and even agglomeration, and irreversible agglomeration and agglomeration caused by Van der Waals force among the particles, thereby improving the dispersibility of the water suspending agent containing the pyraclostrobin and the epoxiconazole and the stability in the long-term storage process.

2. The water suspending agent containing the pyraclostrobin and the epoxiconazole is used by further adding an EO-PO block copolymer to be combined with the carboxylate on the basis of using the carboxylate as a dispersing agent, one section of the components of the block copolymer is a pure EO section, the other section of the components of the block copolymer is a pure PO section, the hydrophilic group is EO, the hydrophobic group is PO, the hydrophilic group is beneficial to wetting of raw pyraclostrobin and epoxiconazole, the pyraclostrobin and the epoxiconazole are easier to wrap, and the particles of the water suspending system containing the pyraclostrobin and the epoxiconazole can prevent the particles from colliding in the wrapping process under the dispersing action of the carboxylate, meanwhile, the spatial positions among the particles are increased, the wrapping rate of the pyraclostrobin and the epoxiconazole can be improved, and the pesticide effect of the water suspending agent is improved. Further, the hydrophobic group of the EO-PO block copolymer can prevent agglomeration among particles, so that the fluidity of the water suspension system containing the pyraclostrobin and the epoxiconazole is improved, and the storage stability of the water suspension agent containing the pyraclostrobin and the epoxiconazole is improved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

Fig. 1 is a flow chart of a preparation method of the water suspending agent containing pyraclostrobin and epoxiconazole in one embodiment.

Detailed Description

To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not represent the only embodiments.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The water suspending agent containing pyraclostrobin and epoxiconazole in one embodiment comprises the following components in parts by mass: 10-25 parts of pyraclostrobin, 5-15 parts of epoxiconazole, 1-4 parts of EO-PO block copolymer wetting agent, 6-12 parts of carboxylate dispersant, 1.4-3.2 parts of thickening agent and 35-72 parts of deionized water.

The water suspending agent containing the pyraclostrobin and the epoxiconazole is compounded with the pyraclostrobin and the epoxiconazole, so that the water suspending agent is high in systemic speed, high in pesticide effect and long in lasting period. The carboxylate dispersant is adopted as the dispersant in the water suspending agent containing the pyraclostrobin and the epoxiconazole, the comb-shaped structure of the carboxylate is favorable for the spatial repulsion between particles in the water suspending agent containing the pyraclostrobin and the epoxiconazole, so that the water suspending agent containing the pyraclostrobin and the epoxiconazole can generate better steric hindrance effect, and prevent the particles from being collided during Brownian motion to cause flocculation and agglomeration of the particles in a dispersed phase and even agglomeration, and irreversible agglomeration and agglomeration caused by Van der Waals force among the particles, thereby improving the dispersibility of the water suspending agent containing the pyraclostrobin and the epoxiconazole and the stability in the long-term storage process. Furthermore, on the basis of using carboxylate as a dispersing agent, an EO-PO block copolymer is added to be combined with the carboxylate for use, one section of the components of the block copolymer is a pure EO section, the other section of the components of the block copolymer is a pure PO section, wherein the hydrophilic group is EO, the hydrophobic group is PO, and the hydrophilic group is beneficial to the wetting of raw pesticide pyraclostrobin and epoxiconazole, so that the pyraclostrobin and the epoxiconazole are easier to be wrapped. Furthermore, the hydrophobic group of the EO-PO block copolymer can prevent agglomeration among particles, so that the fluidity of the water suspension system containing the pyraclostrobin and the epoxiconazole is improved, and the storage stability of the water suspension agent containing the pyraclostrobin and the epoxiconazole is improved. In addition, the thickening agent can improve the viscosity of the water suspension system containing the pyraclostrobin and the epoxiconazole, so that the water suspension agent containing the pyraclostrobin and the epoxiconazole has better fluidity and is not easy to agglomerate and cake, and the storage stability of the water suspension agent containing the pyraclostrobin and the epoxiconazole is improved.

In one embodiment, the EO-PO block copolymer wetting agent is10500、Pluronic F127、Ethylan NAt least one of S-500LQ, Ethylan 324 and ULTRASURF 8070.

In one embodiment, the carboxylate dispersant is at least one of SP-75Y, Sokalan-CP9, GERONON T/36, Atlox4913, and TERSPERSE 2500.

In one embodiment, the thickener comprises xanthan gum, magnesium aluminum silicate and white carbon black. The water suspending agent containing pyraclostrobin and epoxiconazole is a coarse dispersion system, is easy to settle original drug particles under the action of gravity, belongs to an unstable suspension system, and has the problem of suspension stability. According to the Stokes sedimentation formula, the thickening agent is added into the water suspending agent containing the pyraclostrobin and the epoxiconazole, so that the viscosity of the water suspending system containing the pyraclostrobin and the epoxiconazole can be adjusted, and the sedimentation of raw drug particles in the storage process is reduced. However, the thickener tends to increase the viscosity of the aqueous suspension system and to cause foaming and unstable viscosity. In order to reduce foams in the water suspension system of pyraclostrobin and epoxiconazole and improve the stability of the water suspension system of pyraclostrobin and epoxiconazole, in the embodiment, the thickening agent comprises xanthan gum, magnesium aluminum silicate and white carbon black, xanthan gum sol molecules can form super-bonded banded spiral copolymer to form a fragile gel-like network structure, the shapes of solid particles, liquid drops and bubbles can be supported, and the emulsion stabilizing effect and the suspension capacity are high. However, when xanthan gum is used alone as a thickener, the problem that the viscosity of an aqueous suspension system is too high and foam is increased easily occurs. In this embodiment, magnesium aluminum silicate and white carbon black are added to be used in cooperation with xanthan gum, the magnesium aluminum silicate is a hydrophilic colloid and has pseudoplastic fluidity, and the viscosity of the water suspension system of pyraclostrobin and epoxiconazole can be well adjusted to prevent overhigh viscosity. The white carbon black has a three-dimensional network structure due to good chemical stability and hydrogen bonds formed among silanol groups, and the viscosity of a dispersion system is increased to play a role in preventing sedimentation. Through the cooperation of the magnesium aluminum silicate, the white carbon black and the xanthan gum, the viscosity of the water suspension system of the pyraclostrobin and the epoxiconazole can be increased, and the settling speed of particles can be prevented and delayed, so that the layering and precipitation of the water suspension agent of the pyraclostrobin and the epoxiconazole are improved, the foam in the water suspension system of the pyraclostrobin and the epoxiconazole can be inhibited, and the stability of the water suspension system of the pyraclostrobin and the epoxiconazole is improved.

Further, the mass ratio of the xanthan gum to the magnesium aluminum silicate to the white carbon black is (0.1-0.2): (0.3-1): (1-2). In this embodiment, by controlling the mass ratio of xanthan gum, magnesium aluminum silicate and white carbon black, the viscosity of the water suspending agent of pyraclostrobin and epoxiconazole can be further controlled, and the settling rate of particles can be prevented and delayed, so that the layering and precipitation of the water suspending agent of pyraclostrobin and epoxiconazole are improved, and the stability of the water suspending system of pyraclostrobin and epoxiconazole is improved. In addition, the mass ratio of the xanthan gum to the magnesium aluminum silicate to the white carbon black is controlled to be (0.1-0.2): (0.3-1): (1-2), the thixotropy of magnesium aluminum silicate and the three-dimensional network structure of white carbon black can sufficiently inhibit the foaming rate of xanthan gum and other wetting dispersants, and the foam in the water suspension system of pyraclostrobin and epoxiconazole can be effectively inhibited. It should be noted that, in the preparation process of the water suspending agent containing pyraclostrobin and epoxiconazole, xanthan gum, magnesium aluminum silicate and white carbon black are added into the water suspending system containing pyraclostrobin and epoxiconazole at different stages, the magnesium aluminum silicate and white carbon black are added in the grinding process of the water suspending system containing pyraclostrobin and epoxiconazole, and the xanthan gum is added after the grinding of the water suspending system containing pyraclostrobin and epoxiconazole is finished. The magnesium aluminum silicate and the white carbon black are added in the grinding process, so that the viscosity of a system can be increased, and the settling velocity of particles can be prevented and delayed, thereby improving the layering and precipitation of the suspending agent. And the grinding aid can also play a role in auxiliary grinding, so that the grinding efficiency is increased. The magnesium aluminum silicate has good thixotropic body, can prevent the situation that the pipeline is blocked because the sedimentation speed of raw medicine particles is high before the grinding process, and can prevent the sample from being solidified because of overhigh viscosity of the sample when the water suspension system containing the pyraclostrobin and the epoxiconazole is ground due to the thixotropy of the magnesium aluminum silicate, thereby playing the effect of grinding assistance. Furthermore, the white carbon black has better chemical stability, and hydrogen bonds can be formed among silanol groups, so that a three-dimensional net structure is generated, the viscosity of a dispersion system is increased to play a role in preventing sedimentation, and the effect of auxiliary grinding is further achieved. After the grinding, add xanthan gum, xanthan gum macromolecule special construction and colloidal characteristic, enable the system stable, be difficult for subsiding, and add xanthan gum after grinding, can avoid at the grinding in-process, because the effect of mechanical stress, and lead to the colloidal structure to be destroyed to guarantee the stability of the water suspension system that contains pyraclostrobin and epoxiconazole.

In one embodiment, the water suspending agent containing pyraclostrobin and epoxiconazole further comprises the following components in parts by mass: 3-5 parts of an antifreezing agent. As can be understood, crops are easy to cause frostbite in the low-temperature environment in winter, and certain bacteria, such as ice nucleus bacteria, can be generated and propagated in the low-temperature environment, and induce the water of plant cells to freeze at the temperature of between 2 ℃ below zero and 3 ℃ below zero to generate frost. In order to improve the frost resistance of the water suspending agent containing pyraclostrobin and epoxiconazole and crops, in the embodiment, the water suspending agent containing pyraclostrobin and epoxiconazole further comprises 3-5 parts by mass of an antifreezing agent. The antifreezing agent can activate biological enzyme, kill or prevent ice nucleus bacteria from generating and propagating, maintain the structural stability of the biological membrane during cooling, reduce and lighten the damage of low temperature to the membrane, reduce the freezing point value of plant cells, enhance the water retention and freezing resistance of plants, inhibit and destroy frozen protein, increase heat, reduce freezing capacity and improve the resistance of the plants to low temperature.

Further, the antifreeze is at least one of ethylene glycol, propylene glycol and polyethylene glycol. The freezing point of the solution formed by the glycol and the water is low, the condensation point is lower, the lowest freezing point of the glycol is about-60 ℃, the lowest condensation point is-75 ℃, and therefore, the lowest freezing resistance of the glycol antifreeze fluid is-75 ℃. The polyethylene glycol is a high polymer of ethylene glycol, has better antifreezing performance, and the aqueous solution of the polyethylene glycol can also be used as a suspending agent, which is beneficial to improving the stability of the microcapsule suspending agent. The combination of the polyethylene glycol and the emulsifier can increase the stability of the emulsifier. The freezing point of the propylene glycol is as low as-59 ℃, the boiling point is as high as 187 ℃, and the propylene glycol has good freezing resistance and strong anti-boiling performance. The propylene glycol antifreezing agent belongs to a biodegradable product and has better environmental protection property.

In one embodiment, the water suspending agent containing pyraclostrobin and epoxiconazole further comprises the following components in parts by mass: 0.1 to 0.5 portion of defoaming agent. It can be understood that the water suspension system of the pyraclostrobin and the epoxiconazole is easy to generate more air bubbles in the preparation and grinding process, and the air bubbles are easy to interfere with the preparation of the water suspension agent containing the pyraclostrobin and the epoxiconazole, so that the dispersion uniformity of the raw pesticide is influenced. In order to improve the dispersion uniformity of the water suspension system containing the pyraclostrobin and the epoxiconazole, in the embodiment, the defoaming agent is added to destroy the elasticity of the membrane to cause the breaking of bubbles, and the defoaming agent is added to the foam system to diffuse to a gas-liquid interface, so that the surfactant with a foam stabilizing effect is difficult to recover the elasticity of the membrane, the effect of eliminating bubbles is achieved, and the dispersion uniformity of the water suspension system containing the pyraclostrobin and the epoxiconazole is further improved.

In one embodiment, the water suspending agent containing pyraclostrobin and epoxiconazole further comprises the following components in parts by mass: 0.1 to 0.5 portion of preservative. It is understood that the preservative can inhibit the activity of microorganisms, prevent the deterioration of the microcapsule suspension, and simultaneously act as a bactericide for crops. In the embodiment, components in the water suspending agent containing the pyraclostrobin and the epoxiconazole, such as xanthan gum serving as a thickening agent, are easy to deteriorate, so that the drug effect of the water suspending agent containing the pyraclostrobin and the epoxiconazole is influenced, and through the action of the preservative, the deterioration of each component in the water suspending agent containing the pyraclostrobin and the epoxiconazole can be prevented, so that the storage stability of the water suspending agent containing the pyraclostrobin and the epoxiconazole is improved.

The invention also provides a preparation method of the water suspending agent containing the pyraclostrobin and the epoxiconazole, which is used for preparing the water suspending agent containing the pyraclostrobin and the epoxiconazole in any embodiment, and comprises the following steps: mixing an EO-PO block copolymer wetting agent, a carboxylate dispersant, a thickening agent, an antifreezing agent and a first preset amount of deionized water, and stirring for the first time to obtain a first mixture; adding pyraclostrobin and epoxiconazole into the first mixture to obtain a second mixture; grinding the second mixture to obtain a third mixture; mixing xanthan gum, a defoaming agent, a preservative and a first preset amount of deionized water to obtain a fourth mixture; and adding the fourth mixture into the third mixture, and stirring for the second time to obtain the water suspending agent containing the pyraclostrobin and the epoxiconazole.

In order to better understand the preparation method of the water suspending agent containing pyraclostrobin and epoxiconazole, the preparation method of the water suspending agent containing pyraclostrobin and epoxiconazole is further explained as follows, and referring to fig. 1, the preparation method of the water suspending agent containing pyraclostrobin and epoxiconazole of one embodiment specifically comprises the following steps:

s100, mixing the EO-PO segmented copolymer wetting agent, the carboxylate dispersant, the thickening agent, the antifreezing agent and a first preset amount of deionized water, and stirring for the first time to obtain a first mixture.

In this embodiment, the EO-PO block copolymer wetting agent, the carboxylate dispersant, the thickener, and the antifreeze are all auxiliaries of an aqueous suspension containing pyraclostrobin and epoxiconazole, and the auxiliaries are added into deionized water first to be stirred and mixed, so that the EO-PO block copolymer wetting agent, the carboxylate dispersant, the thickener, and the antifreeze are fully and uniformly dissolved in the deionized water, thereby facilitating the subsequent addition of raw medicines pyraclostrobin and epoxiconazole, and enabling the pyraclostrobin and epoxiconazole to fully react with the wetting agent, the dispersant, the thickener, and the antifreeze. In this embodiment, the first predetermined amount is 60% to 70% of the total amount of the deionized water by mass in the aqueous suspension containing pyraclostrobin and epoxiconazole, so as to sufficiently dissolve the EO-PO block copolymer wetting agent, the carboxylate dispersant, the thickener and the antifreeze.

S200, adding pyraclostrobin and epoxiconazole into the first mixture to obtain a second mixture.

In this example, pyraclostrobin and epoxiconazole were added to the first mixture which was mixed uniformly, so that pyraclostrobin and epoxiconazole could be well dissolved in the first mixture. Further, in the mixing process, stirring operation is carried out simultaneously, so that the dissolving efficiency of the pyraclostrobin and the epoxiconazole and the uniformity of the second mixture are effectively improved, and further grinding of the raw pyraclostrobin and the epoxiconazole is facilitated.

And S300, grinding the second mixture to obtain a third mixture.

In this embodiment, the second mixture is ground to uniformly disperse the solid active compound insoluble or slightly soluble in water, so as to form the water suspending agent containing pyraclostrobin and epoxiconazole, which has fine particles, high suspension and good fluidity. Further, the thickening agents in the embodiment are magnesium aluminum silicate and white carbon black, and the magnesium aluminum silicate and the white carbon black can increase the viscosity of the system and prevent and delay the settling velocity of particles in the grinding process, so that the layering and precipitation of the suspending agent are improved. And the grinding aid can also play a role in auxiliary grinding, so that the grinding efficiency is increased. The magnesium aluminum silicate has good thixotropic body, can prevent the situation that the pipeline is blocked because the sedimentation speed of raw medicine particles is high before the grinding process, and can prevent the sample from being solidified because of overhigh viscosity of the sample when the water suspension system containing the pyraclostrobin and the epoxiconazole is ground due to the thixotropy of the magnesium aluminum silicate, thereby playing the effect of grinding assistance. Furthermore, the white carbon black has better chemical stability, and hydrogen bonds can be formed among silanol groups, so that a three-dimensional net structure is generated, the viscosity of a dispersion system is increased to play a role in preventing sedimentation, and the effect of auxiliary grinding is further achieved.

S400, mixing xanthan gum, a defoaming agent, a preservative and a second preset amount of deionized water to obtain a fourth mixture.

In this embodiment, add xanthan gum after the grinding, xanthan gum macromolecule special construction and colloidal characteristic enable the system stable, are difficult for subsiding, and add xanthan gum after the grinding, can avoid at the grinding in-process, because the effect of mechanical stress, and lead to the colloidal structure to be destroyed to guarantee the stability of the water suspension system that contains pyraclostrobin and epoxiconazole. Furthermore, the defoaming agent is added into a foam system and diffuses towards a gas-liquid interface, so that the surfactant with a foam stabilizing effect is difficult to recover the membrane elasticity, the effect of eliminating bubbles is achieved, and the dispersion uniformity of the water suspension system containing the pyraclostrobin and the epoxiconazole is improved. Through the action of the preservative, the components in the water suspending agent containing the pyraclostrobin and the epoxiconazole can be prevented from deteriorating, and the storage stability of the water suspending agent containing the pyraclostrobin and the epoxiconazole is further improved. Furthermore, through the action of the preservative, the components in the water suspending agent containing the pyraclostrobin and the epoxiconazole can be prevented from deteriorating, and the storage stability of the water suspending agent containing the pyraclostrobin and the epoxiconazole is further improved. In this embodiment, the second predetermined amount is 30% to 40% of the total amount of the deionized water by mass in the aqueous suspension containing pyraclostrobin and epoxiconazole, so as to sufficiently dissolve xanthan gum, the antifoaming agent and the preservative.

And S500, adding the fourth mixture into the third mixture, and carrying out secondary stirring operation to obtain the water suspending agent containing pyraclostrobin and epoxiconazole.

In this embodiment, the fourth mixture is added to the third mixture, so that the uniformly dissolved technical solution and the uniformly dissolved additive solution are sufficiently and uniformly mixed together, and the dispersibility of the aqueous suspension system containing pyraclostrobin and epoxiconazole is improved through the second stirring operation, so as to obtain the aqueous suspension agent containing pyraclostrobin and epoxiconazole.

In one embodiment, the preparation method of the water suspension containing the pyraclostrobin and the epoxiconazole further comprises the following steps after the step of adding the pyraclostrobin and the epoxiconazole to the first mixture to obtain the second mixture and before the step of grinding the second mixture to obtain the third mixture: the second mixture is subjected to a first homogeneous dispersion operation. It is understood that after the step of adding pyraclostrobin and epoxiconazole to the first mixture to obtain the second mixture, local aggregation of particles in the system of the second mixture is likely to occur, thereby being disadvantageous for subsequent grinding operations of the second mixture. In order to improve the grinding uniformity of the second mixture, in this embodiment, before the grinding operation is performed on the second mixture, the first homogeneous dispersion operation is performed on the second mixture, so as to improve the dispersibility and uniformity of the raw pesticide pyraclostrobin and epoxiconazole in the second mixture system, thereby facilitating the further grinding of the second mixture, and further improving the stability of the aqueous suspension containing pyraclostrobin and epoxiconazole.

Further, the time of the first homogeneous dispersion operation is 20 minutes to 30 minutes. It is understood that if the time of the first homogeneous dispersion operation is too short, the dispersibility of the second mixture tends to be poor; if the time of the first homogenizing and dispersing operation is too long, high temperature is easy to generate, so that the second mixture is scorched and crystallized, and even the drug effects of the raw pesticide pyraclostrobin and epoxiconazole are damaged. In this embodiment, the time of the first homogeneous dispersion operation is 20 minutes to 30 minutes, which enables the second mixture to achieve better dispersibility, and ensures the drug effects of the raw pesticide pyraclostrobin and epoxiconazole.

In one embodiment, the grinding operation includes a rough grinding operation and a sanding operation. In this embodiment, the second mixture is first coarsely ground, so that the large particles in the second mixture are first primarily ground, thereby facilitating further fine grinding and preventing the problems of uneven particle size and too large particle size caused by one-time grinding. After coarse grinding is carried out by a colloid mill, the second mixture is transferred to a horizontal sand mill for sand grinding operation, so that the second mixture after coarse grinding is further finely ground, the particle size of the second mixture, namely the particle size in the water suspension containing the pyraclostrobin and the epoxiconazole is effectively reduced, the uniformity of the particle size is improved, the settling speed of the particles is further delayed, the layering and precipitation of the water suspending agent are improved, and the dispersibility and stability of the water suspending agent are improved.

Further, the sanding operation is divided into a primary sanding operation and a secondary sanding operation. It can be understood that the pyraclostrobin has a low melting point of 40-60 ℃, and if the grinding temperature is high, recrystallization is easily caused. And the grinding time is too long, so that the grinding temperature is easy to rise, the recrystallization of the pyraclostrobin is caused, and the storage and the use of the water suspending agent containing the pyraclostrobin and the epoxiconazole are not facilitated. In order to improve the stability of technical pyraclostrobin in the grinding process, in this embodiment, the sanding operation divide into one-level sanding operation and second grade sanding operation, the second mixture that will accomplish the corase grind operation is transferred to horizontal sand mill and is carried out one-level sanding operation earlier, then carry out second grade sanding operation with the second mixture, through the second mixing branch second grade sanding with after the corase grind, the problem that the temperature that can avoid once only sanding to bring is too high, prevent that pyraclostrobin from taking place the recrystallization phenomenon because of the high temperature, thereby improve the stability of the aqueous suspension containing pyraclostrobin and epoxiconazole. In addition, divide into one-level sanding operation and second grade sanding operation with the sanding operation, can make the particle grinding in the water suspension that contains pyraclostrobin and epoxiconazole to more meticulous and even. In this embodiment, through the secondary sanding operation, the particle size of the particles in the water suspension system containing pyraclostrobin and epoxiconazole is less than 4 microns, according to the Stokes formula, the settling velocity of the raw drug particles is in direct proportion to the square of the particle diameter, the particle diameter of the raw drug particles less than 4 microns is beneficial to delaying the settling velocity of the particles, improving the layering and precipitation of the water suspension agent, and the smaller the particle size is, the more beneficial the water suspension agent containing pyraclostrobin and epoxiconazole is to be adhered to the surface of a plant, so that the use efficacy of the water suspension agent containing pyraclostrobin and epoxiconazole is improved.

Further, the polishing temperature is 30 ℃ or lower. It can be understood that the pyraclostrobin has a low melting point of 40-60 ℃, and if the temperature of the grinding environment is high, recrystallization is easily caused. In order to ensure the stability of the water suspension system containing pyraclostrobin and epoxiconazole in the grinding process, in the embodiment, the temperature of the grinding environment is controlled to be below 30 ℃, so that the temperature of the grinding environment is lower than the melting point of raw pesticide pyraclostrobin, the problems that the raw pesticide is melted due to the fact that slurry containing pyraclostrobin generates heat in the grinding process, and recrystallization occurs when the slurry is recovered to normal temperature are solved, and the stability of the water suspension system containing pyraclostrobin and epoxiconazole in the grinding process is improved.

In one embodiment, the preparation method of the aqueous suspension containing pyraclostrobin and epoxiconazole further comprises the following steps of, after the step of mixing xanthan gum, an antifoaming agent, a preservative and a second preset amount of deionized water to obtain a fourth mixture, and before the step of adding the fourth mixture into the third mixture and performing a second stirring operation to obtain the aqueous suspension containing pyraclostrobin and epoxiconazole: and carrying out second homogeneous dispersion operation on the fourth mixture. It will be appreciated that after the mixing of the xanthan gum, the antifoaming agent, the preservative and the second predetermined amount of deionized water to provide the fourth mixture, local aggregation of particles in the fourth mixture system is likely to occur, thereby affecting the dispersibility and uniformity of the fourth mixture system. In order to improve the dispersibility and uniformity of the fourth mixture system, in this embodiment, before the third mixture is added to the fourth mixture, the fourth mixture is subjected to a second homogeneous dispersion operation, so that the dispersibility and uniformity of the fourth mixture system are improved, the third mixture is more easily fused after being added, a more uniform water suspension system containing pyraclostrobin and epoxiconazole is obtained, and the preparation efficiency of the water suspension agent containing pyraclostrobin and epoxiconazole is improved.

Further, the time of the second homogeneous dispersion operation is 10 minutes to 15 minutes. It is understood that if the time of the second homogeneous dispersion operation is too short, the dispersibility of the fourth mixture tends to be poor; if the time of the second homogenizing and dispersing operation is too long, high temperature is easily generated, so that the fourth mixture is scorched or the auxiliary agent is deteriorated, such as damage to xanthan gum, in this embodiment, the time of the first homogenizing and dispersing operation is 20 minutes to 30 minutes, so that the fourth mixture can achieve better dispersibility, and the auxiliary agent effects of xanthan gum, the defoaming agent and the preservative in the fourth mixture can be ensured.

In one embodiment, the second stirring operation is carried out for a period of time ranging from 15 minutes to 20 minutes. It can be understood that after the fourth mixture is added into the third mixture, a second stirring operation is performed to obtain the water suspending agent containing the pyraclostrobin and the epoxiconazole with better dispersibility and uniformity. If the time of the second stirring operation is too short, the obtained water suspending agent containing pyraclostrobin and epoxiconazole has poor dispersibility and uniformity; if the time of the second stirring operation is too long, the water suspension system containing the pyraclostrobin and the epoxiconazole is easy to damage. In this embodiment, the time of the second stirring operation is 15 minutes to 20 minutes, which can effectively improve the dispersibility and uniformity of the aqueous suspension containing pyraclostrobin and epoxiconazole, and simultaneously ensure the stability of each effective component in the aqueous suspension system containing pyraclostrobin and epoxiconazole.

Example 1

Adding 40.10 wt% of deionized water, 7 wt% of GERONON T/36, 2 wt% of Pluronic F127, 2 wt% of Ethylan NS-500LQ, 3 wt% of ethylene glycol, 1 wt% of magnesium aluminum silicate and 2 wt% of white carbon black into a reaction vessel in sequence, and uniformly stirring. Adding 10 wt% of pyraclostrobin and 5 wt% of epoxiconazole, homogenizing for 20 minutes by a homogenizer, coarsely grinding by a colloid mill, transferring to a horizontal sand mill for secondary grinding, wherein the grinding temperature is below 30 ℃, and the grinding particle size D98 is not more than 4 mu m. And after grinding, uniformly mixing the residual 26.74 wt% of deionized water, 0.16 wt% of xanthan gum, 0.5 wt% of defoaming agent and 0.5 wt% of preservative, homogenizing for 10 minutes by using a homogenizer, adding the mixture into the ground material while stirring, and stirring for 15 minutes to obtain the pyraclostrobin and epoxiconazole pesticide composition suspending agent.

Example 2

Mixing 37.2 wt% of deionized water, 2 wt% of Ethylan NS-500LQ and 2 wt% of10500. 6 weight percent of SP-75Y, 5 weight percent of propylene glycol, 1 weight percent of magnesium aluminum silicate and 1 weight percent of white carbon black are sequentially added into a reaction vessel and stirred uniformly. Adding 15 wt% of pyraclostrobin and 5 wt% of epoxiconazole, homogenizing for 30 minutes by a homogenizer, coarsely grinding by a colloid mill, transferring to a horizontal sand mill for secondary grinding, wherein the grinding temperature is below 30 ℃, and the grinding particle size D98 is not more than 4 mu m. And after grinding, uniformly mixing the rest 24.8 wt% of deionized water, 0.2 wt% of xanthan gum, 0.5 wt% of defoaming agent and 0.3 wt% of preservative, homogenizing for 15 minutes by using a homogenizer, adding the mixture into the ground material while stirring, and stirring for 20 minutes to obtain the pyraclostrobin and epoxiconazole pesticide composition suspending agent.

Example 3

31.85 wt% of deionized water, 5 wt% of TERSPERSE 2500, 3 wt% of ULTRASURF8070, 3 wt% of propylene glycol, 2 wt% of polyethylene glycol, 0.3 wt% of magnesium aluminum silicate and 2 wt% of white carbon black are sequentially added into a reaction vessel and stirred uniformly. Adding 20 wt% of pyraclostrobin and 10 wt% of epoxiconazole, homogenizing for 25 minutes by a homogenizer, coarsely grinding by a colloid mill, transferring to a horizontal sand mill for secondary grinding, wherein the grinding temperature is below 30 ℃, and the grinding particle size D98 is not more than 4 mu m. And after grinding, uniformly mixing the residual 21.23 wt% of deionized water, 0.12 wt% of xanthan gum, 0.3 wt% of defoaming agent and 0.2 wt% of preservative, homogenizing for 12 minutes by using a homogenizer, adding the mixture into the ground material while stirring, and stirring for 17 minutes to obtain the pyraclostrobin and epoxiconazole pesticide composition suspending agent.

Example 4

35.52 wt% of deionized water, 2 wt% of Pluronic F127, 2 wt% of Ethyllan NS-500LQ, 2 wt% of Atlox4913, 3 wt% of polyethylene glycol, 0.5 wt% of magnesium aluminum silicate and 1 wt% of white carbon black are sequentially added into a reaction vessel and stirred uniformly. Adding 25 wt% of pyraclostrobin and 5 wt% of epoxiconazole, homogenizing for 25 minutes by a homogenizer, coarsely grinding by a colloid mill, transferring to a horizontal sand mill for secondary grinding, wherein the grinding temperature is below 30 ℃, and the grinding particle size D98 is not more than 4 mu m. And after grinding, uniformly mixing the residual 23.68 wt% of deionized water, 0.1 wt% of xanthan gum, 0.1 wt% of defoaming agent and 0.1 wt% of preservative, homogenizing for 12 minutes by using a homogenizer, adding the mixture into the ground material while stirring, and stirring for 17 minutes to obtain the pyraclostrobin and epoxiconazole pesticide composition suspending agent.

Comparative example 1

Mixing 37.2 wt% of deionized water, 2 wt% of Ethylan NS-500LQ and 2 wt% of10500. 6 weight percent of SP-75Y, 5 weight percent of propylene glycol, 1 weight percent of magnesium aluminum silicate and 1 weight percent of white carbon black are sequentially added into a reaction vessel and stirred uniformly. Adding 15 wt% of pyraclostrobin and 5 wt% of epoxiconazole, homogenizing for 30 minutes by a homogenizer, coarsely grinding by a colloid mill, and transferring to a horizontal sand mill for secondary grinding, wherein the grinding temperature is 35 ℃, and the grinding particle size D98 is not more than 4 mu m. After the grinding is finished, the rest 24.8 wt% of deionized water and 0.2 wt% of deionized water are addedUniformly mixing xanthan gum, 0.5 wt% of defoaming agent and 0.3 wt% of preservative, homogenizing for 15 minutes by using a homogenizer, adding the mixture into the ground material while stirring, and stirring for 20 minutes to obtain the pyraclostrobin and epoxiconazole pesticide composition suspending agent.

Comparative example 2

Mixing 37.2 wt% of deionized water, 2 wt% of Ethylan NS-500LQ and 2 wt% of10500. 6 wt% of SP-75Y and 5 wt% of propylene glycol are sequentially added into a reaction vessel and stirred uniformly. Adding 15 wt% of pyraclostrobin and 5 wt% of epoxiconazole, homogenizing for 30 minutes by a homogenizer, coarsely grinding by a colloid mill, and transferring to a horizontal sand mill for secondary grinding, wherein the grinding temperature is 35 ℃, and the grinding particle size D98 is not more than 4 mu m. And after grinding, uniformly mixing the rest 24.8 wt% of deionized water, 0.2 wt% of xanthan gum, 1 wt% of magnesium aluminum silicate, 1 wt% of white carbon black, 0.5 wt% of defoaming agent and 0.3 wt% of preservative, homogenizing for 15 minutes by using a homogenizer, adding the homogenized mixture into the ground material while stirring, and stirring for 20 minutes to obtain the pyraclostrobin and epoxiconazole pesticide composition suspending agent.

Comparative example 3

Mixing 37.2 wt% of deionized water, 2 wt% of Ethylan NS-500LQ and 2 wt% of10500. 6 wt% of SP-75Y and 5 wt% of propylene glycol are sequentially added into a reaction vessel and stirred uniformly. Adding 15 wt% of pyraclostrobin and 5 wt% of epoxiconazole, homogenizing for 30 minutes by a homogenizer, coarsely grinding by a colloid mill, and transferring to a horizontal sand mill for secondary grinding, wherein the grinding temperature is 35 ℃, and the grinding particle size D98 is 5 mu m. And after grinding, uniformly mixing the rest 24.8 wt% of deionized water, 0.2 wt% of xanthan gum, 1 wt% of magnesium aluminum silicate, 1 wt% of white carbon black, 0.5 wt% of defoaming agent and 0.3 wt% of preservative, homogenizing for 15 minutes by using a homogenizer, adding the homogenized mixture into the ground material while stirring, and stirring for 20 minutes to obtain the pyraclostrobin and epoxiconazole pesticide composition suspending agent.

The performance tests of the water suspending agent containing pyraclostrobin and epoxiconazole prepared in examples 1 to 4 and the water suspending agent containing pyraclostrobin and epoxiconazole prepared in comparative examples 1 to 3 are performed as follows, and the test results are shown in tables 1 and 2, wherein table 1 is the test result of the water suspending agent containing pyraclostrobin and epoxiconazole prepared in examples 1 to 4, and table 2 is the test result of the water suspending agent containing pyraclostrobin and epoxiconazole prepared in examples 2 and 1 to 3:

TABLE 1

TABLE 2

As can be seen from tables 1 and 2, the particle sizes of the aqueous suspending agents containing pyraclostrobin and epoxiconazole, prepared according to examples 1 to 5, after heat storage are smaller than those of the aqueous suspending agents containing pyraclostrobin and epoxiconazole, prepared according to comparative examples 1 to 3, and the storage stability of the aqueous suspending agent containing pyraclostrobin and epoxiconazole is better. Compared with the example 2, the comparative example 1 has the advantages that the grinding temperature is different, so that the particle size of the aqueous suspending agent containing pyraclostrobin and epoxiconazole in the comparative example 1 after heat storage is larger than that of the example 2, and the grinding temperature is controlled to be 30 ℃ so as to avoid crystallization of raw pyraclostrobin and improve the dispersibility and stability of the aqueous suspending agent containing pyraclostrobin and epoxiconazole. Compared with the example 2, the comparative example 2 shows that the addition sequence of the white carbon black and the magnesium aluminum silicate in the preparation process is different, so that the particle size of the aqueous suspending agent containing the pyraclostrobin and the epoxiconazole in the comparative example 2 after the thermal storage is larger than that of the example 2, and the dispersibility and the stability of the aqueous suspending agent containing the pyraclostrobin and the epoxiconazole are better. Compared with example 2, the comparative example 3 shows that the particle size of the particles in the aqueous suspension system is larger due to the fact that the particle grinding particle size DV98 in the comparative example 3 is larger than 4 microns, and 3% of water is analyzed out, so that the aqueous suspension agent of pyraclostrobin and epoxiconazole has better stability.

Compared with the prior art, the invention has at least the following advantages:

1. the water suspending agent containing the pyraclostrobin and the epoxiconazole is prepared by compounding the pyraclostrobin and the epoxiconazole, so that the water suspending agent has the advantages of high internal absorption speed, high drug effect and long lasting period. The carboxylate dispersant is adopted as the dispersant in the water suspending agent containing the pyraclostrobin and the epoxiconazole, the comb-shaped structure of the carboxylate is favorable for the spatial repulsion between particles in the water suspending agent containing the pyraclostrobin and the epoxiconazole, so that the water suspending agent containing the pyraclostrobin and the epoxiconazole can generate better steric hindrance effect, and prevent the particles from being collided during Brownian motion to cause flocculation and agglomeration of the particles in a dispersed phase and even agglomeration, and irreversible agglomeration and agglomeration caused by Van der Waals force among the particles, thereby improving the dispersibility of the water suspending agent containing the pyraclostrobin and the epoxiconazole and the stability in the long-term storage process.

2. The water suspending agent containing the pyraclostrobin and the epoxiconazole is used by further adding an EO-PO block copolymer to be combined with the carboxylate on the basis of using the carboxylate as a dispersing agent, one section of the components of the block copolymer is a pure EO section, the other section of the components of the block copolymer is a pure PO section, the hydrophilic group is EO, the hydrophobic group is PO, the hydrophilic group is beneficial to wetting of raw pyraclostrobin and epoxiconazole, the pyraclostrobin and the epoxiconazole are easier to wrap, and the particles of the water suspending system containing the pyraclostrobin and the epoxiconazole can prevent the particles from colliding in the wrapping process under the dispersing action of the carboxylate, meanwhile, the spatial positions among the particles are increased, the wrapping rate of the pyraclostrobin and the epoxiconazole can be improved, and the pesticide effect of the water suspending agent is improved. Further, the hydrophobic group of the EO-PO block copolymer can prevent agglomeration among particles, so that the fluidity of the water suspension system containing the pyraclostrobin and the epoxiconazole is improved, and the storage stability of the water suspension agent containing the pyraclostrobin and the epoxiconazole is improved.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.