阅读说明：本技术 一种包含啶磺草胺和异丙隆的复合除草剂 (Compound herbicide containing pyroxsulam and isoproturon ) 是由 刘言合 陈琦 于 2021-10-09 设计创作，主要内容包括：本发明公开了一种包含啶磺草胺和异丙隆的复合除草剂,包括如下重量份原料：啶磺草胺1-30份、异丙隆10-80份、安全剂微球20-30份、余量为辅助成分；该安全剂微球以安全剂为原料进行微球化处理,微球化处理后使得安全剂微球不易出现流失,安全剂以壳聚糖为基体,作物吸收壳聚糖,能够增强自身的生理生化机制,促使根系发达,茎叶粗壮,使作物吸收和利用水肥的能力以及光合作用提升,同时中间体5的双苯噁唑酸结构能够防止作物多啶磺草胺和异丙隆的吸收,进而降低了除草剂对作物的影响,保证了作物产率。(The invention discloses a compound herbicide containing pyroxsulam and isoproturon, which comprises the following raw materials in parts by weight: 1-30 parts of pyroxsulam, 10-80 parts of isoproturon, 20-30 parts of safener microspheres and the balance of auxiliary components; the safener microspheres are subjected to microsphericization treatment by taking a safener as a raw material, the safener microspheres are not easy to run off after the microsphericization treatment, the safener takes chitosan as a substrate, crops absorb the chitosan, the physiological and biochemical mechanism of the crops can be enhanced, the root system is promoted to be developed, stem leaves are thick and strong, the capacity of the crops for absorbing and utilizing water and fertilizer and photosynthesis are improved, meanwhile, the isoxadifen structure of the intermediate 5 can prevent the absorption of the crop pyroxsulam and isoproturon, the influence of the herbicide on the crops is further reduced, and the crop yield is ensured.)

1. A composite herbicide comprising pyroxsulam and isoproturon, characterized in that: the feed comprises the following raw materials in parts by weight: 1-30 parts of pyroxsulam, 10-80 parts of isoproturon, 20-30 parts of safener microspheres and the balance of auxiliary components;

the safener microsphere is prepared by the following steps:

step A1: dissolving the safener in acetic acid, stirring, adding liquid paraffin and span 80, uniformly mixing, heating and stirring, adding a glutaraldehyde aqueous solution, continuously stirring, cooling to room temperature, centrifuging to remove a supernatant, washing a substrate for 3 times by using petroleum ether, and drying to obtain the safener microspheres.

2. The compound herbicide containing pyroxsulam and isoproturon as claimed in claim 1, wherein: the dosage ratio of the safener, acetic acid, liquid paraffin, span 80 and glutaraldehyde aqueous solution is 0.08g:10mL:50mL:5mL:1 mL.

3. The compound herbicide containing pyroxsulam and isoproturon as claimed in claim 1, wherein: the safety agent is prepared by the following steps:

step B1: mixing tetrahydrofuran, acetophenone and phenyl magnesium bromide for reaction, cooling, adding a saturated ammonium chloride aqueous solution, stirring for reaction to obtain an intermediate 1, adding the intermediate 1 and a sulfuric acid solution into a reaction kettle, performing reflux reaction until the reaction solution is yellow, adding concentrated nitric acid and concentrated sulfuric acid, and reacting to obtain an intermediate 2;

step B2: uniformly mixing aminoacetic acid and ethanol, stirring, dropwise adding thionyl chloride, performing reflux reaction after dropwise adding is finished to prepare an intermediate 3, dissolving the intermediate 3 in deionized water, adding concentrated hydrochloric acid and sodium nitrite aqueous solution, and reacting to prepare an intermediate 4;

step B3: adding the intermediate 2 and the intermediate 4 into a reaction kettle, dropwise adding a sodium carbonate aqueous solution, stirring, adding tin powder and concentrated hydrochloric acid, reacting, and adjusting the pH value of a reaction solution to obtain an intermediate 5;

step B4: adding chitosan into dimethyl sulfoxide, stirring, adding sodium hydroxide solution, stirring, adding chloroacetic acid, heating for reaction to obtain carboxymethyl chitosan, dissolving carboxymethyl chitosan in deionized water, adding intermediate 4 and 1-hydroxybenzotriazole, and reacting to obtain the safener.

4. The compound herbicide containing pyroxsulam and isoproturon as claimed in claim 3, wherein: the dosage ratio of the tetrahydrofuran, the acetophenone, the phenyl magnesium bromide and the saturated ammonium chloride aqueous solution in the step B1 is 5mL:2.3g:3.1g:20mL, and the dosage ratio of the intermediate 1, the sulfuric acid solution, the concentrated sulfuric acid and the concentrated nitric acid is 1g:5mL:2.5mL:3 mL.

5. The compound herbicide containing pyroxsulam and isoproturon as claimed in claim 3, wherein: the dosage ratio of the aminoacetic acid, the ethanol and the thionyl chloride in the step B2 is 2g:12.5mL:4.3g, and the dosage ratio of the intermediate 3, the deionized water, the concentrated hydrochloric acid and the sodium nitrite aqueous solution is 2g:6mL:1.3mL:10 mL.

6. The compound herbicide containing pyroxsulam and isoproturon as claimed in claim 3, wherein: the dosage ratio of the intermediate 2, the intermediate 4, the sodium carbonate aqueous solution, the tin powder and the concentrated hydrochloric acid in the step B3 is 1g:1.5g:5 mL.

7. The compound herbicide containing pyroxsulam and isoproturon as claimed in claim 3, wherein: in the step B4, the dosage ratio of the chitosan, the dimethyl sulfoxide, the sodium hydroxide solution and the chloroacetic acid is 1g to 10mL to 6mL to 5g, and the dosage mass ratio of the carboxymethyl chitosan, the intermediate 5 and the 1-hydroxybenzotriazole is 3:1: 1.2.

Technical Field

The invention relates to the technical field of herbicide preparation, and particularly relates to a compound herbicide containing pyroxsulam and isoproturon.

Background

The pyroxsulam is a systemic conduction type herbicide for winter wheat field after seedling emergence, can effectively prevent and kill annual gramineous weeds in wheat fields such as alopecurus, Japanese alopecurus, bromus and the like, and can also inhibit weeds such as hardwood, wild oat, lolium multiflorum, wild agrimony, speedwell and the like.

Isoproturon is a systemic conduction type selective herbicide and is absorbed by the root system and young leaves of weeds. Can be used for preventing and killing gramineous weeds such as alopecurus, physalis quinata, beckmelon and hardwood and partial broadleaf weeds such as chickweed, caraway and cardamine hirsute in winter wheat field.

The existing compound herbicide of pyroxsulam and isoproturon has a certain weeding effect, but when weeds absorb the herbicide, wheat can also absorb the herbicide, so that the wheat is poisoned, the wheat is dead, and the yield of the wheat is influenced.

Disclosure of Invention

The invention aims to provide a compound herbicide containing pyroxsulam and isoproturon, and solves the problem that the yield of wheat is reduced due to the compound herbicide at the present stage through safety agent microspheres.

The purpose of the invention can be realized by the following technical scheme:

a composite herbicide containing pyroxsulam and isoproturon comprises the following raw materials in parts by weight: 1-30 parts of pyroxsulam, 10-80 parts of isoproturon, 20-30 parts of safener microspheres and the balance of auxiliary components;

the compound herbicide is prepared by uniformly mixing the raw materials;

furthermore, the auxiliary component is one or a mixture of a plurality of dispersing agents, disintegrating agents, water-soluble organic solvents and fillers in any ratio, and can be selected according to the prepared pesticide dosage form.

Furthermore, the formulation of the compound herbicide containing pyroxsulam and isoproturon is water suspending agent, dispersible oil suspending agent, wettable powder, water dispersible granule, emulsion in water, missible oil and microemulsion.

Further, the safener microspheres are prepared by the following steps:

step A1: dissolving a safener in acetic acid, stirring and adding liquid paraffin and span 80 under the condition that the rotation speed is 150-200r/min, uniformly mixing, heating to 50-60 ℃, stirring for 2-4h, adding a glutaraldehyde aqueous solution, continuously stirring for 3-5h, cooling to room temperature, centrifuging to remove supernatant, washing a substrate for 3 times by using petroleum ether, and drying to obtain the safener microsphere.

Further, the dosage ratio of the safener, acetic acid, liquid paraffin, span 80 and glutaraldehyde aqueous solution is 0.08g:10mL:50mL:5mL:1mL, and the mass fraction of the glutaraldehyde aqueous solution is 50%.

Further, the safety agent is prepared by the following steps:

step B1: adding tetrahydrofuran, acetophenone and phenyl magnesium bromide into a reaction kettle, reacting for 4-6h at the rotation speed of 150-200r/min and the temperature of 50-60 ℃, cooling to room temperature, adding a saturated ammonium chloride aqueous solution at the temperature of 0-3 ℃, stirring for 1-1.5h to prepare an intermediate 1, adding the intermediate 1 and a sulfuric acid solution into the reaction kettle, performing reflux reaction until the reaction liquid is yellow, adding concentrated nitric acid and concentrated sulfuric acid, and reacting for 1-1.5h at the temperature of 50-55 ℃ to prepare an intermediate 2;

the reaction process is as follows:

step B2: uniformly mixing aminoacetic acid and ethanol, stirring and dropwise adding thionyl chloride under the conditions that the rotation speed is 150-200r/min and the temperature is minus 3-5 ℃, heating to 65-70 ℃ after dropwise adding, carrying out reflux reaction for 2-3h to obtain an intermediate 3, dissolving the intermediate 3 in deionized water, adding concentrated hydrochloric acid and sodium nitrite aqueous solution under the condition that the temperature is 1-3 ℃, and carrying out reaction for 3-5h to obtain an intermediate 4;

the reaction process is as follows:

step B3: adding the intermediate 2 and the intermediate 4 into a reaction kettle, dropwise adding a sodium carbonate aqueous solution under the condition of the temperature of 5-10 ℃, stirring for 2-3h, adding tin powder and concentrated hydrochloric acid, reacting for 30-40min under the conditions of the rotation speed of 200-300r/min and the temperature of 80-90 ℃, and adjusting the pH value of a reaction solution to 9-10 to prepare an intermediate 5;

the reaction process is as follows:

step B4: adding chitosan into dimethyl sulfoxide, stirring and adding a sodium hydroxide solution under the conditions that the rotation speed is 200-35 ℃ and the temperature is 25-35 ℃, stirring for 2-3h, adding chloroacetic acid, heating to 60-70 ℃, reacting for 3-5h to obtain carboxymethyl chitosan, dissolving the carboxymethyl chitosan into deionized water, adding an intermediate 4 and 1-hydroxybenzotriazole, and reacting for 5-7h under the conditions that the rotation speed is 150-200r/min and the temperature is 35-40 ℃ to obtain the safener.

Further, the amount ratio of the tetrahydrofuran, the acetophenone, the phenyl magnesium bromide and the saturated ammonium chloride aqueous solution in the step B1 is 5mL:2.3g:3.1g:20mL, the amount ratio of the intermediate 1, the sulfuric acid solution, the concentrated sulfuric acid and the concentrated nitric acid is 1g:5mL:2.5mL:3mL, the mass fraction of the sulfuric acid solution is 20%, the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the concentrated nitric acid is 68%.

Furthermore, the dosage ratio of the glycine, the ethanol and the thionyl chloride in the step B2 is 2g:12.5mL:4.3g, the dosage ratio of the intermediate 3, the deionized water, the concentrated hydrochloric acid and the sodium nitrite aqueous solution is 2g:6mL:1.3mL:10mL, the mass fraction of the concentrated hydrochloric acid is 36%, and the mass fraction of the sodium nitrite aqueous solution is 20%.

Furthermore, the using amount ratio of the intermediate 2, the intermediate 4, the sodium carbonate aqueous solution, the tin powder and the concentrated hydrochloric acid in the step B3 is 1g:1.5g:5mL, the mass fraction of the sodium carbonate aqueous solution is 8%, and the concentrated hydrochloric acid is the same as that in the step B2.

Further, in the step B4, the dosage ratio of the chitosan, the dimethyl sulfoxide, the sodium hydroxide solution and the chloroacetic acid is 1g to 10mL to 6mL to 5g, the mass fraction of the sodium hydroxide solution is 75%, and the dosage ratio of the carboxymethyl chitosan, the intermediate 5 and the 1-hydroxybenzotriazole is 3 to 1 to 1.2.

The invention has the beneficial effects that: the invention discloses a compound herbicide containing pyroxsulam and isoproturon, which is prepared by taking pyroxsulam and isoproturon as main raw materials, so that the prepared herbicide has good weeding effect, and safety agent microspheres are prepared at the same time, wherein the safety agent microspheres are prepared by taking a safety agent as a raw material to carry out microsphericization treatment, so that the safety agent microspheres are not easy to lose after the microsphericization treatment, the function of the safety agent microspheres is ensured, the safety agent takes acetophenone and phenylmagnesium bromide as raw materials to react to prepare an intermediate 1, the intermediate 1 is treated with sulfuric acid solution and then is subjected to nitration treatment to prepare an intermediate 2, aminoacetic acid is treated to form hydrochloride to prepare an intermediate 3, the intermediate 3 is further treated to prepare an intermediate 4, the intermediate 2 and the intermediate 4 are reacted and then are reduced to prepare an intermediate 5, chitosan is subjected to carboxylation treatment, the preparation method comprises the steps of preparing carboxymethyl chitosan, reacting the carboxymethyl chitosan with an intermediate 5 to enable carboxyl on the carboxymethyl chitosan and amino on the intermediate 5 to be subjected to dehydration condensation, and preparing the safety agent.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A composite herbicide containing pyroxsulam and isoproturon comprises the following raw materials in parts by weight: 1 part of pyroxsulam, 10 parts of isoproturon, 20 parts of safener microspheres and the balance of auxiliary components;

the compound herbicide is prepared by uniformly mixing the raw materials;

the safener microsphere is prepared by the following steps:

step A1: dissolving a safener in acetic acid, stirring and adding liquid paraffin and span 80 under the condition that the rotating speed is 150r/min, uniformly mixing, heating to 50 ℃, stirring for 2h, adding a glutaraldehyde aqueous solution, continuously stirring for 3h, cooling to room temperature, centrifuging to remove supernatant, washing a substrate with petroleum ether for 3 times, and drying to obtain the safener microsphere.

The safety agent is prepared by the following steps:

step B1: adding tetrahydrofuran, acetophenone and phenyl magnesium bromide into a reaction kettle, reacting for 4 hours at the rotation speed of 150r/min and the temperature of 50 ℃, cooling to room temperature, adding a saturated ammonium chloride aqueous solution at the temperature of 0 ℃, stirring for 1 hour to prepare an intermediate 1, adding the intermediate 1 and a sulfuric acid solution into the reaction kettle, performing reflux reaction until the reaction liquid is yellow, adding concentrated nitric acid and concentrated sulfuric acid, and reacting for 1 hour at the temperature of 50 ℃ to prepare an intermediate 2;

step B2: uniformly mixing aminoacetic acid and ethanol, stirring and dropwise adding thionyl chloride under the conditions that the rotating speed is 150r/min and the temperature is minus 3 ℃, heating to 65 ℃ after dropwise adding, carrying out reflux reaction for 2 hours to obtain an intermediate 3, dissolving the intermediate 3 in deionized water, adding concentrated hydrochloric acid and sodium nitrite aqueous solution under the condition that the temperature is 1 ℃, and carrying out reaction for 3 hours to obtain an intermediate 4;

step B3: adding the intermediate 2 and the intermediate 4 into a reaction kettle, dropwise adding a sodium carbonate aqueous solution at the temperature of 5 ℃, stirring for 2 hours, adding tin powder and concentrated hydrochloric acid, reacting for 30 minutes at the rotation speed of 200r/min and the temperature of 80 ℃, and adjusting the pH value of the reaction solution to 9 to obtain an intermediate 5;

step B4: adding chitosan into dimethyl sulfoxide, stirring and adding a sodium hydroxide solution under the conditions that the rotating speed is 200r/min and the temperature is 25 ℃, stirring for 2 hours, adding chloroacetic acid, heating to 60 ℃, reacting for 3 hours to obtain carboxymethyl chitosan, dissolving the carboxymethyl chitosan into deionized water, adding intermediate 5 and 1-hydroxybenzotriazole, and reacting for 5 hours under the conditions that the rotating speed is 150r/min and the temperature is 35 ℃ to obtain the safener.

Example 2

A composite herbicide containing pyroxsulam and isoproturon comprises the following raw materials in parts by weight: 20 parts of pyroxsulam, 50 parts of isoproturon, 25 parts of safener microspheres and the balance of auxiliary components;

the compound herbicide is prepared by uniformly mixing the raw materials;

the safener microsphere is prepared by the following steps:

step A1: dissolving a safener in acetic acid, stirring and adding liquid paraffin and span 80 under the condition that the rotating speed is 180r/min, uniformly mixing, heating to 55 ℃, stirring for 3h, adding a glutaraldehyde aqueous solution, continuously stirring for 4h, cooling to room temperature, centrifuging to remove supernatant, washing a substrate with petroleum ether for 3 times, and drying to obtain the safener microsphere.

The safety agent is prepared by the following steps:

step B1: adding tetrahydrofuran, acetophenone and phenyl magnesium bromide into a reaction kettle, reacting for 5 hours at the rotation speed of 180r/min and the temperature of 55 ℃, cooling to room temperature, adding a saturated ammonium chloride aqueous solution at the temperature of 2 ℃, stirring for 1.3 hours to prepare an intermediate 1, adding the intermediate 1 and a sulfuric acid solution into the reaction kettle, performing reflux reaction until the reaction solution is yellow, adding concentrated nitric acid and concentrated sulfuric acid, and reacting for 1.3 hours at the temperature of 53 ℃ to prepare an intermediate 2;

step B2: uniformly mixing aminoacetic acid and ethanol, stirring and dropwise adding thionyl chloride under the conditions that the rotating speed is 180r/min and the temperature is 4 ℃ below zero, heating to 68 ℃ after dropwise adding, carrying out reflux reaction for 2.5 hours to obtain an intermediate 3, dissolving the intermediate 3 in deionized water, adding concentrated hydrochloric acid and sodium nitrite aqueous solution under the temperature of 2 ℃, and carrying out reaction for 4 hours to obtain an intermediate 4;

step B3: adding the intermediate 2 and the intermediate 4 into a reaction kettle, dropwise adding a sodium carbonate aqueous solution at the temperature of 8 ℃, stirring for 2.5h, adding tin powder and concentrated hydrochloric acid, reacting for 35min at the rotation speed of 200r/min and the temperature of 85 ℃, and adjusting the pH value of a reaction solution to 10 to obtain an intermediate 5;

step B4: adding chitosan into dimethyl sulfoxide, stirring and adding a sodium hydroxide solution under the conditions that the rotating speed is 300r/min and the temperature is 30 ℃, stirring for 2.5 hours, adding chloroacetic acid, heating to 65 ℃, reacting for 4 hours to obtain carboxymethyl chitosan, dissolving the carboxymethyl chitosan into deionized water, adding intermediate 5 and 1-hydroxybenzotriazole, and reacting for 6 hours under the conditions that the rotating speed is 180r/min and the temperature is 38 ℃ to obtain the safety agent.

Example 3

A composite herbicide containing pyroxsulam and isoproturon comprises the following raw materials in parts by weight: 30 parts of pyroxsulam, 80 parts of isoproturon, 30 parts of safener microspheres and the balance of auxiliary components;

the compound herbicide is prepared by uniformly mixing the raw materials;

the safener microsphere is prepared by the following steps:

step A1: dissolving a safener in acetic acid, stirring and adding liquid paraffin and span 80 under the condition that the rotating speed is 200r/min, uniformly mixing, heating to the temperature of 60 ℃, stirring for 4h, adding a glutaraldehyde aqueous solution, continuously stirring for 5h, cooling to room temperature, centrifuging to remove supernatant, washing a substrate with petroleum ether for 3 times, and drying to obtain the safener microsphere.

The safety agent is prepared by the following steps:

step B1: adding tetrahydrofuran, acetophenone and phenyl magnesium bromide into a reaction kettle, reacting for 6 hours at the rotation speed of 200r/min and the temperature of 60 ℃, cooling to room temperature, adding a saturated ammonium chloride aqueous solution at the temperature of 3 ℃, stirring for 1.5 hours to prepare an intermediate 1, adding the intermediate 1 and a sulfuric acid solution into the reaction kettle, performing reflux reaction until the reaction solution is yellow, adding concentrated nitric acid and concentrated sulfuric acid, and reacting for 1.5 hours at the temperature of 55 ℃ to prepare an intermediate 2;

step B2: uniformly mixing aminoacetic acid and ethanol, stirring and dropwise adding thionyl chloride under the conditions that the rotating speed is 200r/min and the temperature is minus 5 ℃, heating to 70 ℃ after dropwise adding, carrying out reflux reaction for 3 hours to obtain an intermediate 3, dissolving the intermediate 3 in deionized water, adding concentrated hydrochloric acid and sodium nitrite aqueous solution under the condition that the temperature is 3 ℃, and carrying out reaction for 5 hours to obtain an intermediate 4;

step B3: adding the intermediate 2 and the intermediate 4 into a reaction kettle, dropwise adding a sodium carbonate aqueous solution under the condition of the temperature of 10 ℃, stirring for 3 hours, adding tin powder and concentrated hydrochloric acid, reacting for 40 minutes under the conditions of the rotating speed of 300r/min and the temperature of 90 ℃, and adjusting the pH value of the reaction solution to 10 to obtain an intermediate 5;

step B4: adding chitosan into dimethyl sulfoxide, stirring and adding a sodium hydroxide solution under the conditions that the rotating speed is 300r/min and the temperature is 35 ℃, stirring for 3 hours, adding chloroacetic acid, heating to 70 ℃, reacting for 5 hours to obtain carboxymethyl chitosan, dissolving the carboxymethyl chitosan into deionized water, adding intermediate 5 and 1-hydroxybenzotriazole, and reacting for 7 hours under the conditions that the rotating speed is 200r/min and the temperature is 40 ℃ to obtain the safener.

Comparative example 1

Compared with example 1, the comparative example does not add the safener microspheres, and the rest steps are the same.

Comparative example 2

Compared with the example 1, the chitosan is used for replacing the safener microspheres in the comparative example, and the rest steps are the same.

Comparative example 3

This comparison is the herbicidal composition disclosed in chinese patent CN 105284846A.

The test crop is wheat, the control object is wheat field gramineous weeds, the weeds are applied in the 3-5 leaf period, the test field is flat in shape, the soil is loam, the fertility is moderate, the pH value is 7.2, 30 square meters are arranged in each cell, 30 cells are arranged in total, the cells are randomly arranged in blocks, the survival rate of the wheat and the weed control rate are calculated by adopting a conventional spraying method and applying 45kg of pesticide per mu, and the results are shown in the following table;

from the above table, it can be seen that the control rate of the composite herbicide prepared in the examples 1-3 on weeds is 98.2-98.5%, and the survival rate of wheat is 93.5-94.1%, which indicates that the composite herbicide prepared by the invention has a good weeding effect, and meanwhile, the safener microspheres can effectively prevent wheat from excessively absorbing pyroxsulam and isoproturon, so that the normal growth of wheat is ensured.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.