CN116420730A - Water-emulsifiable paste for preventing and removing resistant gramineous weeds in paddy field and preparation method thereof - Google Patents

Abstract

The embodiment of the invention discloses a water-emulsifiable paste for preventing and killing resistant gramineous weeds in a paddy field and a preparation method thereof. The paste comprises the following components in percentage by weight: 1-4% of Tolpyralate, 12.5-50% of propanil, 3-5% of cloquintocet-mexyl, 10-30% of emulsifying agent, 5-10% of dispersing agent, 0.1-0.5% of defoaming agent and the balance of carrier; wherein, the mass ratio of Tolpyralate, propanil and cloquintocet-mexyl is 1.8-2.1:24-26:3-5. The paste provided by the invention can well prevent and remove the resistant gramineous weeds in the paddy field, is safe to the paddy field, has very high market value, and solves the problems of poor safety, resource waste, environmental hazard, incomplete grass death and the like in the process of preventing and removing the resistant gramineous weeds in the paddy field of the existing medicament.

Description

Water-emulsifiable paste for preventing and removing resistant gramineous weeds in paddy field and preparation method thereof

Technical Field

The embodiment of the invention relates to the technical field of pesticides, in particular to a water-emulsifiable paste for preventing and killing resistant gramineous weeds in a paddy field and a preparation method thereof.

Background

Tolpyralate is a trione herbicide, test code SL-573, molecular formula C ₂₁ H ₂₈ N ₂ O ₉ S, relative molecular mass 484.52, CAS number: 1101132-67-5. Chemical name: 1- ({ 1-ethyl-4- [ (2-methyl-3-methoxyethoxy-4-methanesulfonyl) benzoyl]-1H-pyrazol-5-yl } oxy) ethyl methyl carbonate. The mechanism of action is to inhibit p-hydroxyphenylpyruvate dioxygenase (HPPD), ultimately affecting carotenoid biosynthesis in plants, which is highly safe to corn due to its slow rate of absorption by corn and its ability to rapidly degrade Tolpyrate to inactive compounds via 4-hydroxylation. The metabolic capacity of the rice to Tolpyralate is weak, and the Tolpyralate is sprayed through stems and leaves to be applied, so that the rice is easy to generate phytotoxicity.

Propanil is an amide contact herbicide, is hardly conducted in plants, is used for preventing and killing the barnyard grass of a paddy field through stem and leaf spraying, and is reported to be in the form of emulsifiable concentrate, dispersible oil suspending agent, water dispersible granule, suspending agent and the like at present, but the emulsifiable concentrate and the dispersible oil suspending agent contain a large amount of organic solvents, and serious harm is brought to production and users in the processing and using processes, and soil and water source pollution is caused, so that ecological environment is destroyed; the water dispersible granule and the suspending agent are not accepted by the market all the time due to poor drug effect, and weeds are easy to rebound after application due to the fact that propanil does not have systemic conduction activity, so that dead weeds are not thorough and easy to recur.

The ointment is a water-based ointment preparation containing active ingredients and capable of forming a film, and is generally used directly. Dosage form code "PA", often referred to as a paste in terms of set. Patent CN201410117869.4 discloses a pesticide paste for controlling longhorn beetles. The paste can only be directly used, can not be emulsified and dispersed after being mixed with water, and can not meet the requirement of spraying pesticides.

At present, as single herbicide is used in paddy fields for successive years, the difficulty in preventing and controlling resistant grassy weeds such as paddy field resistant barnyard grass, resistant moleplant seeds and resistant crabgrass is increased, and the resistance of paddy field weeds is widely paid attention to by the industry personnel. Therefore, it is of great importance to develop a water emulsifiable paste for controlling resistant grassy weeds in paddy fields.

Disclosure of Invention

Therefore, the embodiment of the invention provides a water-emulsifiable paste for preventing and killing resistant gramineous weeds in a paddy field and a preparation method thereof, and aims to solve the problems of poor safety, resource waste, environmental hazard, incomplete grass death and the like in the process of preventing and killing resistant gramineous weeds in the paddy field of the existing medicament.

In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:

according to a first aspect of the embodiments of the present invention, there is provided a water-emulsifiable paste for controlling resistant grassy weeds in paddy fields, the paste comprising, in weight percent: 1-4% of Tolpyralate, 12.5-50% of propanil, 3-5% of cloquintocet-mexyl, 10-30% of emulsifying agent, 5-10% of dispersing agent, 0.1-0.5% of defoaming agent and the balance of carrier, wherein the mass ratio of Tolpyralate, propanil and cloquintocet-mexyl is 1.8-2.1:24-26:3-5.

The inventor finds that the paste provided by the invention has excellent stability and water dispersibility by taking Tolpyralate and propanil as active ingredients and taking the detoxicated quindox as a safener under the dosage proportion, and has excellent safety and efficacy on rice when a stem and leaf spraying mode is adopted, so that the problem of phytotoxicity on rice when the Tolpyralate is sprayed on the stem and leaf is solved, and the problems of incomplete death of the propanil after the application of the pesticide and environmental protection are solved. In some preferred embodiments, the mass ratio of Tolpyralate, propanil to cloquintocet-mexyl is 2:25:3-5.

Further, the emulsifier consists of the following components in percentage by mass of 1.8-2.2:0.8-1.2:0.8-1.2 of dodecylbenzene sulfonic triethanolamine salt, EO/PO block copolymer and castor oil polyoxyethylene ether. The research shows that the emulsifier can also improve the preventing and killing performance of the paste on the resistant gramineous weeds in the paddy field on the premise of ensuring the dispersion stability of the paste. In some preferred embodiments, the mass ratio of triethanolamine dodecylbenzenesulfonate, EO/PO block copolymer, and castor oil polyoxyethylene ether is 2:1:1.

further, the EO/PO block copolymer is Ethylans-500 LQ, atlas ^TM G-5000 or terminator 5500.

Further, the number of ethylene oxide of the castor oil polyoxyethylene ether is 25-40.

Further, the castor oil polyoxyethylene ether is Emulson CO-25, emulson CO-30, emulson CO-36 or Emulson CO-40.

Further, the dispersant is naphthalene sulfonate dispersant Morwet D-425, morwet D-400 or Supragil MNS/90.

Further, the defoamer is a silicone defoamer Sag1522 or Sag1572.

Further, the carrier is fumed silica, precipitated silica, kaolin or attapulgite.

According to a second aspect of the embodiments of the present invention, there is provided a method for preparing a paste as defined in any one of the above, comprising the steps of:

adding Tolpyralate, propanil, cloquintocet-mexyl and a dispersing agent into a mixing kettle, uniformly mixing, and crushing to a first particle size by a jet mill to obtain a material A;

adding the material A into a shearing kettle, adding an emulsifying agent, a defoaming agent and a carrier, and shearing uniformly to obtain a material B;

and grinding the material B to a second particle size by a colloid mill to obtain the paste.

Further, the median particle diameter of the first particle diameter/the second particle diameter is 2 to 10 micrometers.

The embodiment of the invention has the following advantages:

1. the ointment provided by the invention has good stability, can be rapidly emulsified and dispersed after being put into water, can be placed for a long time, can not generate the phenomena of oil slick, precipitation and the like, ensures that the liquid medicine is sprayed more uniformly, is favorable for the exertion of the drug effect, reduces the phytotoxicity of rice and has high safety.

2. Compared with the traditional emulsifiable concentrates and dispersible oil suspending agents, the ointment provided by the invention does not contain organic solvents, and reduces the pollution of the solvents to the environment and the waste of resources; compared with suspending agents and water dispersible granules, the water dispersible granule has better drug effect and very high market value.

Detailed Description

Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. In the following examples and comparative examples, all percentages are by weight unless otherwise indicated.

Example 1

The embodiment provides a paste, which comprises the following raw materials: 2% of Tolpyralate, 25% of propanil, 4% of cloquintocet-mexyl, 30% of emulsifying agent, 30% of Morwet D-4005%, sag15220.1%, 5% of precipitated white carbon black and the balance of attapulgite, wherein the emulsifying agent comprises triethanolamine dodecylbenzenesulfonate, termul 5500 and Emulson CO-25 according to a mass ratio of 2:1:1.

The preparation method of the paste comprises the following steps:

adding Tolpyralate, propanil, cloquintocet-mexyl and a dispersing agent into a mixing kettle, uniformly mixing, and crushing to a first particle size (the median particle size is 2-10 microns) through a jet mill to obtain a material A; adding the material A into a shearing kettle, adding an emulsifying agent, a defoaming agent and a carrier, and shearing uniformly to obtain a material B; grinding the material B to a second particle size (median particle size of 2-10 microns) by a colloid mill to obtain the paste.

The following examples and comparative examples were prepared in the same manner as in example 1.

Example 2

The embodiment provides a paste, which comprises the following raw materials: 2% of Tolpyralate, 25% of propanil, 3% of cloquintocet-mexyl, 30% of emulsifying agent, 30% of Morwet D-4255%, 20.1% of Sag1521%, 5% of fumed silica and the balance of attapulgite; wherein the emulsifier is composed of triethanolamine dodecylbenzene sulfonate, ethyl lan NS-500LQ and Emulson CO-40 according to the mass ratio of 2:1:1.

Example 3

The embodiment provides a paste, which comprises the following raw materials: tolpyralate 2%, propanil 25%, cloquintocet-mexyl 5%, emulsifying agent 15%, morwet D-4005%, sag15220.1%, fumed silica 5%, and attapulgite for the rest, wherein the emulsifying agent is triethanolamine salt of dodecylbenzenesulfonic acid, atlas ^TM G-5000 and Emulson CO-36 in a mass ratio of 2:1:1.

Example 4

The embodiment provides a paste, which comprises the following raw materials: 2% of Tolpyralate, 25% of propanil, 4% of cloquintocet-mexyl, 10% of emulsifying agent, 10% of Supragil MNS/905, 20.1% of Sag15720.1% of precipitated white carbon black and the balance of attapulgite, wherein the emulsifying agent consists of triethanolamine dodecylbenzenesulfonate and Atlas ^TM G-5000 according to the mass ratio of 2: 1.

Example 5

The embodiment provides a paste, which comprises the following raw materials: tolpyralate 2%, propanil 25%, cloquintocet-mexyl 5%, emulsifying agent 15%, morwet D-4005%, sag15220.1%, fumed silica 5%, and attapulgite for the rest, wherein the emulsifying agent is triethanolamine salt of dodecylbenzenesulfonic acid, atlas ^TM G-5000 and Emulson CO-36 in a mass ratio of 1:1: 1.

Comparative example 1

The comparative example provides a paste, which comprises the following raw materials: 2% of Tolpyralate, 25% of propanil, 1% of cloquintocet-mexyl, 30% of emulsifying agent, 30% of Morwet D-4005%, sag15220.1%, 5% of precipitated white carbon black and the balance of attapulgite, wherein the emulsifying agent comprises triethanolamine dodecylbenzenesulfonate, termul 5500 and Emulson CO-25 according to a mass ratio of 2:1:1.

Comparative example 2

The comparative example provides a paste, which comprises the following raw materials: 2% of Tolpyralate, 25% of propanil, 2% of cloquintocet-mexyl, 30% of emulsifying agent, 30% of Morwet D-4005%, sag15220.1%, 5% of precipitated white carbon black and the balance of attapulgite, wherein the emulsifying agent comprises triethanolamine dodecylbenzenesulfonate, termul 5500 and Emulson CO-25 according to the mass ratio of 2:1:1.

Comparative example 3

The comparative example provides a paste, which comprises the following raw materials: 2% of Tolpyralate, 25% of propanil, 6% of cloquintocet-mexyl, 30% of emulsifying agent, 30% of Morwet D-4005%, sag15220.1%, 5% of precipitated white carbon black and the balance of attapulgite, wherein the emulsifying agent comprises triethanolamine dodecylbenzenesulfonate, termul 5500 and Emulson CO-25 according to a mass ratio of 2:1:1.

Comparative example 4

The comparative example provides a paste, which comprises the following raw materials: 2% of Tolpyralate, 25% of propanil, 8% of cloquintocet-mexyl, 30% of a compound emulsifier, 30% of Morwet D-4005%, sag15220.1%, 5% of precipitated white carbon black and the balance of attapulgite, wherein the emulsifier is composed of triethanolamine dodecylbenzenesulfonate, termul 5500 and Emulson CO-25 according to a mass ratio of 2:1:1.

Comparative example 5

The comparative example provides a paste, which comprises the following raw materials: 2% of Tolpyralate, 25% of propanil, 10% of cloquintocet-mexyl, 30% of emulsifying agent, 30% of Morwet D-4005%, sag15220.1%, 5% of precipitated white carbon black and the balance of attapulgite, wherein the emulsifying agent comprises triethanolamine dodecylbenzenesulfonate, termul 5500 and Emulson CO-25 according to a mass ratio of 2:1:1.

Comparative example 6

This comparative example provides a cream which differs from example 1 only in that the safener is different, and the comparative example replaces the cloquintocet-mexyl with an equivalent amount of cyclopropanesulfonamide.

Comparative example 7

This comparative example provides a cream which differs from example 1 only in that the safener is different, and the comparative example replaces cloquintocet-mexyl with an equal amount of clomazone.

Comparative example 8

This comparative example provides a cream which differs from example 1 only in that the safener is different, and the comparative example replaces the cloquintocet-mexyl with an equal amount of bisbenzoxazole acid.

Comparative example 9

This comparative example provides a cream which differs from example 1 only in that the safener is different, and the comparative example replaces cloquintocet-mexyl with an equivalent amount of mexyl pyraclonil.

Comparative example 10

The comparative example provides a paste, which comprises the following raw materials: 2% of Tolpyralate, 25% of propanil, 30% of emulsifying agent, 0.1% of Morwet D-4005% of Sag, 5% of precipitated white carbon black and the balance of attapulgite, wherein the emulsifying agent is triethanolamine salt of dodecylbenzenesulfonic acid: terminal 5500: emulson CO-25 is prepared by the following components in mass ratio of 2:1:1.

Test case

1. Stability performance test

Weighing 500 g of the samples of examples 1-5 respectively, adding into a high-barrier bottle, sealing, placing into a constant temperature box at 54 ℃, and detecting the mass fraction of Tolpyralate, propanil and cloquintocet-mexyl in the samples before and after heat storage by using a high performance liquid chromatograph after 14 days; detecting the pH value of the sample before and after heat storage by a pH meter; and detecting the viscosity of the sample before and after heat storage by using a rotational viscometer, and simultaneously calculating the heat storage decomposition rate of Tolpyralate, propanil and cloquintocet according to the mass fraction of Tolpyralate, propanil and cloquintocet in the sample before and after heat storage. The results of the measurements are shown in tables 1 and 2.

TABLE 1

TABLE 2

The results show that the viscosity and the pH value of the samples of the pastes in examples 1-5 are not greatly changed before and after heat storage, and the decomposition rates of three active ingredients, namely Tolpyralate, propanil and cloquintocet-mexyl after heat storage are less than 5 percent.

2. Physical and chemical index test

1 g of each of the samples of examples 1 to 5 and comparative examples 1 to 5 was weighed, added into 100 ml of standard hard water at 30 ℃ and 342mg/L, gently stirred with a glass rod to observe the dispersibility of the sample, and the dispersed liquid medicine was poured into a centrifuge tube and placed in a constant temperature water bath at 30 ℃ for standing for 1 hour and 24 hours, and then the volume of sediment and oil slick were recorded respectively.

Meanwhile, the precipitation and oil slick volumes were recorded in the same manner as in 80% propanil water dispersible granule (commercial agent), 34% propanil emulsifiable concentrate (commercial agent), 15% Tolpyralate suspension (homemade) and 15% Tolpyralate dispersible oil suspension (homemade), and the results are shown in Table 3.

15% Tolpyralate suspension and 15% Tolpyralate dispersible oil suspension may be prepared according to methods conventional in the art. As an example, a 15% tolpyralate suspension was prepared as follows: 15% of Tolpyralate, 0601% of wetting agent Genapol X, 5% of phosphate dispersant EMULSONAG TRST, 5% of glycol, 1% of magnesium aluminum silicate, 6300.2% of defoamer SAG, 0.1% of pinus koraiensis, 0.2% of xanthan gum and a proper amount of water, uniformly shearing the components, grinding the components by a sand mill until the particle size D90 of the materials is less than or equal to 5 microns, and blending the Tolpyralate to 15% to obtain the 15% Tolpyralate suspending agent.

The preparation method of the 15% Tolpyralate dispersible oil suspending agent comprises the following steps: 15% of Tolpyralate, 9% of pesticide emulsion 500#, 7% of Tween 80, 1.5% of organic bentonite and the balance of methyl esterified soybean oil, shearing the components uniformly, and grinding the components by a sand mill until the particle size D90 of the materials is less than or equal to 5 microns, thus obtaining the 15% Tolpyralate dispersible oil suspending agent.

TABLE 3 results of dispersion stability test

The results show that the pastes of examples 1-5 of the present invention have good dispersibility, are very stable after dilution with water, and do not substantially cause oil slivers and precipitates after 24 hours of storage, wherein examples 1-3 are more preferred; the commercial products have a large amount of sediment after 24 hours of dilution, and part of the products have floating oil.

3. Field efficacy and safety test

Test agent: the pastes of examples 1-5.

Comparative example: the pastes of comparative examples 1-10, 80% propanil water dispersible granule, 34% propanil emulsifiable concentrate, 15% Tolpyralate suspension concentrate, 15% Tolpyralate dispersible oil suspension concentrate.

Test date: 2021, 7 and 6 days

Test site: anhui Funan

The planting mode is as follows: direct seeding rice, 4-leaf stage of rice.

Control object: resistant barnyard grass, resistant moleplant, resistant crabgrass.

The test method comprises the following steps: the field resistant gramineae weeds are selected to be uniformly distributed, the rice grows uniformly in field blocks, and the herbicide is not treated by the stem leaves in the test in the season. Three replicates were set for each treatment at 100 square meters. The medicine applying method adopts a backpack electric sprayer to spray evenly, so as to realize no heavy spraying and no leakage spraying. And observing the growth condition of the rice 7 days after the application, observing the death condition of weeds 14 days after the application, and comparing the safety of each medicament on the rice and the prevention effect on resistant gramineous weeds, wherein the results are shown in Table 4.

TABLE 4 safety and efficacy results

The pastes of examples 1-5 have good control effect on resistant barnyard grass, resistant moleplant seed and resistant Ma Tangzai for 14 days and 21 days after application, and the medicament is safe to rice; the ointment of comparative examples 1-2 has good control effect on resistant barnyard grass, resistant semen Euphorbiae and resistant Ma Tangzai after 14 days and 21 days of application, but the rice leaves have a small amount of albino appearance; the pastes of comparative examples 3 to 5 were safe for rice, but the control effect was somewhat lowered as compared with examples 1 to 5; the pastes of comparative examples 6 to 9 have good control effects on resistant barnyard grass, resistant semen Euphorbiae and resistant Ma Tangzai for 14 days and 21 days after application, but the rice leaves have a small amount of whitening or yellowing phenomenon; the safety of comparative example 10 and the Tolpyralate, propanil and two kinds of medicament combinations of the self-made and purchased safety agent-free Tolpyralate and propanil for the market is poor, the prevention effect on the three kinds of resistant grassy weeds is about 90% in 14 days after the medicament, but the prevention effect on the three kinds of grassy weeds is reduced to about 50% in 21 days after the medicament, namely, the prevention effect on the three kinds of resistant grassy weeds can be better after two weeks after the medicament is used by using the Tolpyralate or propanil singly, but dead grasses are not thorough enough, and after a period of time, the weeds continue to grow and rebound. The ointment provided by the invention is safe to rice, and achieves good control effects on resistant barnyard grass, resistant moleplant and resistant horse Tang Neng 14 days and 21 days after application.

While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (10)

1. A water emulsifiable paste for controlling resistant grassy weeds in paddy fields, characterized in that the paste comprises, in weight percent: 1-4% of Tolpyralate, 12.5-50% of propanil, 3-5% of cloquintocet-mexyl, 10-30% of emulsifying agent, 5-10% of dispersing agent, 0.1-0.5% of defoaming agent and the balance of carrier; wherein, the mass ratio of Tolpyralate, propanil and cloquintocet-mexyl is 1.8-2.1:24-26:3-5.

2. Paste according to claim 1, characterized in that the emulsifier consists of a mass ratio of 1.8-2.2:0.8-1.2:0.8-1.2 of dodecylbenzene sulfonic triethanolamine salt, EO/PO block copolymer and castor oil polyoxyethylene ether.

3. The paste as claimed in claim 2, wherein the EO/PO block copolymer is ethyl an NS-500LQ, atlas ^TM G-5000 or terminator 5500.

4. The paste as claimed in claim 2, wherein the castor oil polyoxyethylene ether has an ethylene oxide amount of 25 to 40.

5. The paste of claim 4, wherein the castor oil polyoxyethylene ether is Emulson CO-25, emulson CO-30, emulson CO-36 or Emulson CO-40.

6. The paste according to claim 1, wherein the dispersant is naphthalene sulfonate dispersant Morwet D-425, morwet D-400 or Supragil MNS/90.

7. The paste according to claim 1, wherein the antifoaming agent is a silicone based antifoaming agent, sag1522 or Sag1572.

8. The paste as claimed in claim 1, wherein the carrier is fumed silica, precipitated silica, kaolin or attapulgite.

9. A method of preparing a paste according to any one of claims 1 to 8, comprising the steps of:

adding Tolpyralate, propanil, cloquintocet-mexyl and a dispersing agent into a mixing kettle, uniformly mixing, and crushing to a first particle size by a jet mill to obtain a material A;

adding the material A into a shearing kettle, adding an emulsifying agent, a defoaming agent and a carrier, and shearing uniformly to obtain a material B;

and grinding the material B to a second particle size by a colloid mill to obtain the paste.

10. The method of claim 9, wherein the median particle size of the first particle size/second particle size is 2-10 microns.