CN107251897B - Low-toxicity cytometaherbicide with high efficiency and high disintegration rate and preparation method thereof - Google Patents
Low-toxicity cytometaherbicide with high efficiency and high disintegration rate and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
Abstract
The invention discloses a low-toxicity cytoblast herbicide with high efficiency and high disintegration rate and a preparation method thereof. In addition, the preparation process is easy to control, the stability of the performance of the prepared dry suspending agent is effectively ensured, the production efficiency is effectively improved, and the production cost is reduced. The efficient low-toxicity cytoblast herbicide with high disintegration rate is prepared from the following raw materials in parts by weight: 810 parts of clopyralid, 120 parts of dispersion auxiliary agent for dry suspension, 40-60 parts of wetting auxiliary agent for dry suspension, 40-60 parts of disintegration auxiliary agent for dry suspension and 2500 parts of water.
Description
Technical Field
The invention relates to a herbicide, in particular to a low-toxicity cytoblast herbicide with high efficiency and high disintegration rate and a preparation method thereof.
Background
The pesticide is an important material for agricultural production, and has the advantages of quick response, good control effect, wide adaptability, high economic benefit and the like when being used for controlling diseases, pests, weeds and the like of plants. However, the pesticide may cause certain harm to the environment, human beings, animals and plants while ensuring the abundant harvest of agricultural production. Some traditional pesticide formulations such as missible oil, wettable powder, powder and the like have potential harm to the environment, human or animals and plants in the production or use process. The formula of the missible oil contains a large amount of organic solvents which are mostly inflammable, explosive and toxic, so that the missible oil has great potential safety hazard in the processes of production, storage, transportation and use, causes pollution to the environment and consumes a large amount of non-renewable resources. With the increasing attention of human beings on environmental protection, the pesticide application has higher requirements, so the dosage forms have corresponding limitations.
The pesticide formulation is developed towards water-based formulation and granulation, the water-based formulation is developed towards the formulations such as aqueous emulsion, suspending agent and the like, and the granulation is developed towards the formulations such as water dispersible granules, dry suspending agent and the like. The dry suspending agent is a new formulation developed on the basis of wettable powder and aqueous suspending agent, integrates the advantages of the wettable powder and the aqueous suspending agent, and overcomes the respective defects. The dry suspending agent can be rapidly disintegrated in water, and has good dispersibility and suspensibility; the active ingredients have fine particles, the agent of unit mass has wide coverage on the surface of crops, and the drug effect is good; no dust flying and good safety; the fluidity is good, and the metering and packaging are convenient; can be made into high-concentration products, and reduce the storage and transportation cost. The dry suspending agent is developed rapidly once coming out, and is one of the dosage forms with the best combination property.
Dry suspending agent (DF) is dehydrated from aqueous suspension system, and is a new formulation with great development prospect, which is essentially the same as water dispersible granule, the difference is that the dry suspending agent is prepared by wet grinding granulation, i.e. the dry suspending agent is processed into aqueous suspending agent and then spray drying granulation is adopted to obtain the finished product, therefore, the appearance is generally in a small sphere shape, while the main stream of the water dispersible granule is dry process, at present, extrusion granulation and fluidized bed granulation are common, and the finished product is in a column shape or a sphere shape.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate and a preparation method thereof.
The technical scheme is as follows:
a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate is prepared from the following raw materials in parts by weight: 810 parts of clopyralid, 120 parts of dispersion auxiliary agent for dry suspension, 40-60 parts of wetting auxiliary agent for dry suspension, 40-60 parts of disintegration auxiliary agent for dry suspension and 2500 parts of water.
The wetting auxiliary agent special for dry suspension is one or a mixture of more of sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether, sorbitan fatty acid ester and sodium sulfosuccinate octyl ester.
Preferably, the wetting aid special for dry suspension is sodium lauryl sulfate.
The special disintegrating aid for dry suspension is one or a mixture of more of ammonium sulfate, calcium chloride, magnesium aluminum silicate, bentonite and cross-linked starch.
Preferably, the disintegration aid special for dry suspension is ammonium sulfate.
The dispersing auxiliary agent special for dry suspension is one or a mixture of more of dialkyl succinic acid sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, fatty alcohol phosphate and lignosulfonate.
Preferably, the dispersing aid special for dry suspension is one or a mixture of alkyl naphthalene sulfonate and lignosulfonate.
Further preferably, the dispersing aid special for dry suspension is sodium methylene dinaphthalene sulfonate and/or sodium lignin sulfonate.
Further preferably, the dispersing aid special for dry suspension is alkylated sodium lignosulfonate. In one embodiment of the invention, the dispersing aid special for dry suspension consists of 25-35wt% of sodium methylene dinaphthalene sulfonate and 65-75wt% of sodium alkylated lignosulfonate.
The preparation process of the alkylated sodium lignosulfonate comprises the following steps: mixing sodium lignosulphonate, laccase, saccharifying enzyme and water according to the mass ratio of (95-105): (1-2): (0.1-0.3): (1100-1300), adjusting the pH to 4-5 with 0.8-1.2mol/L hydrochloric acid aqueous solution, stirring for 15-25 minutes at the rotation speed of 120-180 rpm under the conditions that the microwave power is 300-500W, the microwave frequency is 2400-2500MHz and the temperature is 45-55 ℃, and then heating to 90-100 ℃ for heat preservation for 8-12 minutes to inactivate the enzyme to obtain a reaction solution A; filtering the reaction solution A, and freeze-drying to obtain activated sodium lignosulfonate; mixing activated sodium lignin sulfonate and an alcohol solution according to a mass ratio of 1: (5-15) pouring the mixture into a three-neck flask with a reflux condenser pipe and a thermometer, adjusting the pH to 10-11 by using 0.8-1.2mol/L aqueous solution of sodium hydroxide, adding 1-bromododecane accounting for 15-25% of the weight of the activated sodium lignosulfonate and pyridine accounting for 3-7% of the weight of the activated sodium lignosulfonate, carrying out reflux condensation reaction for 5-10 hours at 75-85 ℃ under the protection of nitrogen, and stopping the reaction to obtain a reaction solution B; and washing the reaction liquid B with petroleum ether to remove unreacted 1-bromododecane, and freeze-drying to obtain the alkylated sodium lignosulfonate.
The alcohol solution is an ethanol water solution, and the mass concentration of the ethanol is 5-15%.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, the dispersing aid special for dry suspension, the wetting aid special for dry suspension and the disintegrating aid special for dry suspension into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 35-45MPa, the homogenizing temperature is 20-30 ℃, and the homogenizing time is 10-20 minutes; then shearing the mixture for 30 to 90 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2500-; mixing the shearing emulsion and zirconia beads with the particle size of 0.5-0.7mm according to the mass ratio of 1: (0.8-1.2) adding the mixture into a sand mill for wet grinding, sampling and determining the particle size every 25-35 minutes until the particle size D90 of a suspension system is less than 5 mu m, and filtering to obtain the aqueous suspension;
s3, spray drying the water suspending agent, wherein the air inlet temperature is 110-3The novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
The technical effects are as follows:
the novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate has the advantages of small average particle size, good dispersion stability, high suspension rate, high efficiency, high disintegration rate, low toxicity, volatilization resistance, drift resistance, more uniform droplet size and the like. In addition, the preparation process is easy to control, the stability of the performance of the prepared dry suspending agent is effectively ensured, the production efficiency is effectively improved, and the production cost is reduced.
Detailed Description
Determination of disintegration: the disintegration time is measured, and is generally defined to be less than 3min as qualified. The method comprises the following steps: adding 0.5g of sample into a 100mL stoppered measuring cylinder filled with 90mL standard hard water at 25 ℃, clamping the middle part of the measuring cylinder, stopping the opening of the measuring cylinder, rotating along the center at the speed of 8r/min until the sample is completely disintegrated in water, and recording the time, namely the disintegration time.
Suspension rate determination is carried out according to MT168, 1.0g of sample is weighed to be accurate to 0.0002g, the sample is placed into a beaker containing 50mL of standard hard water (30 +/-1) DEG C, the sample is shaken by hand for 2min 120 times/min, the suspension is kept still for 13min in a water bath at the same temperature, then the suspension is transferred into a 250mL measuring cylinder preheated to 30 ℃, the 250mL scale line is supplemented by (30 +/-1) DEG C standard hard water, a plug is inserted, the measuring cylinder is turned upside down for 30 times within 1min, then the measuring cylinder is vertically placed in a (30 +/-1) DEG C water bath, after the 30min of standing, 225mL liquid at the upper part is pumped out by a suction pipe, the rest 1/10 suspension and precipitate are transferred into a 100mL volumetric flask, the bottom of the measuring cylinder is washed by 15mL water, the content of active ingredients is determined by an extraction method, the suspension rate is calculated, an HP1100Series high performance liquid chromatograph (with a variable wavelength ultraviolet detector) is used for analyzing and detecting clopyralid, the clopyralid is carried out, the particle size of the clopyralid is measured by a microspectrospiral chromatographic column, the flow rate of a filter, the flow rate of the column is calculated, the flow rate of the clopyralid is adjusted by an ultrasonic wave length of 200 μm of 100mL of a stainless steel column, the stainless steel column is adjusted by a temperature difference of 3.5 mm, the temperature difference of the temperature is not more than or less than 60 mm, the temperature of the temperature.
Determination of heat storage stability: sealing 20g of sample in a 50mL ampoule bottle, placing the ampoule bottle in a constant temperature oven at (54 +/-2) DEG C, storing for 14 days, taking out, and carrying out various performance tests, wherein the thermal storage decomposition rate is required to be less than or equal to 5%.
In the examples, clopyralid is provided by the Tiaoao chemical Co., Ltd. in Guangzhou, and the effective content is more than 95%.
In the examples, sodium lauryl sulfate was provided by Jining Baichuan chemical Co.
The fatty alcohol polyoxyethylene ether is provided by Bai Qian chemical Co., Ltd, and has the model of AEO-7.
The sorbitan fatty acid ester is provided by Haian petrochemical plant of Jiangsu province, and has a model number of T-60.
The sodium sulfosuccinate is provided by Haian petrochemical plant of Jiangsu province, and the model is OT.
In the embodiment, the bentonite is 325-mesh organic bentonite provided by Zhejiang Anjiyu Macro chemical industry Co.
Examples the crosslinked starch is supplied by Shanghai resistant to Current industries, Inc.
In the embodiment, the ammonium sulfate is medical grade analytically pure ammonium sulfate provided by the Gallery Peng color fine chemical industry Co.
In the examples calcium chloride was supplied by Cactus, Inc. of Huayang, Lianhong.
Examples magnesium aluminum silicate is provided by Daxin environmental materials, Inc. of Wuxi.
In the examples, sodium methylene dinaphthalene sulfonate is NNO sodium methylene dinaphthalene sulfonate, a model number of chemical technology ltd.
In the examples, sodium lignosulfonate was provided by chemical technology ltd, dennasunny.
In the examples, laccase was supplied by Anhuku bioengineering, Inc., and the enzyme activity was 10000 u/g.
In the examples, the saccharifying enzyme is provided by Shaanxi Furan Natural products Co., Ltd, and the enzyme activity is 100000 u/g.
Example 1-bromododecane, CAS: 143-15-7.
Examples pyridine, CAS: 110-86-1.
Examples ethanol, CAS: 64-17-5.
In the examples, the homogenizer was an experimental high pressure homogenizer model scientz-150, available from Ningbo New Zealand Biotech Co.
In the examples, the high shear dispersion emulsifier is a tin-free winged-Wei automated equipment manufacturing company, Inc. model number WRL 90.
In the embodiment, the sand mill is a model SDF400 experiment dispersing sand mill manufactured by the chemical machinery of the Shundfukang.
In the examples, the laser particle size analyzer is a Rise-2006 model of science and technology Limited in Jinan province.
The spray dryer in the examples is a spray dryer model LP-2200G from Stannless Lepu instruments, Inc.
Example 1
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of methylene dinaphthalene sodium sulfonate, 50 parts of sodium dodecyl sulfate, 50 parts of ammonium sulfate and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium methylene dinaphthalene sulfonate, sodium dodecyl sulfate and ammonium sulfate into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
Example 2
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of methylene dinaphthalene sodium sulfonate, 50 parts of sodium dodecyl sulfate, 50 parts of calcium chloride and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium methylene dinaphthalene sulfonate, sodium dodecyl sulfate and calcium chloride into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
Example 3
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of methylene dinaphthalene sodium sulfonate, 50 parts of sodium dodecyl sulfate, 50 parts of magnesium aluminum silicate and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium methylene dinaphthalene sulfonate, sodium dodecyl sulfate and aluminum magnesium silicate into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
Example 4
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of methylene dinaphthalene sodium sulfonate, 50 parts of sodium dodecyl sulfate, 50 parts of bentonite and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium methylene dinaphthalene sulfonate, sodium dodecyl sulfate and bentonite into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
Example 5
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of methylene dinaphthalene sodium sulfonate, 50 parts of lauryl sodium sulfate, 50 parts of crosslinked starch and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium methylene dinaphthalene sulfonate, sodium dodecyl sulfate and crosslinked starch into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
Example 6
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of methylene dinaphthalene sodium sulfonate, 50 parts of fatty alcohol-polyoxyethylene ether, 50 parts of ammonium sulfate and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium methylene dinaphthalene sulfonate, fatty alcohol-polyoxyethylene ether and ammonium sulfate into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
Example 7
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of methylene dinaphthalene sodium sulfonate, 50 parts of sorbitan fatty acid ester, 50 parts of ammonium sulfate and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium methylene dinaphthalene sulfonate, sorbitan fatty acid ester and ammonium sulfate into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
Example 8
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of methylene dinaphthalene sodium sulfonate, 50 parts of sodium sulfosuccinate, 50 parts of ammonium sulfate and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium methylene dinaphthalene sulfonate, sodium sulfosuccinate and ammonium sulfate into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
Example 9
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of sodium lignosulphonate, 50 parts of sodium dodecyl sulfate, 50 parts of ammonium sulfate and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium lignosulphonate, sodium dodecyl sulfate and ammonium sulfate into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
Example 10
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 110 parts of sodium alkyl lignosulfonate, 50 parts of sodium dodecyl sulfate, 50 parts of ammonium sulfate and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium alkyl lignosulfonate, sodium dodecyl sulfate and ammonium sulfate into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained.
The preparation process of the alkylated sodium lignosulfonate comprises the following steps: mixing sodium lignin sulfonate, laccase, saccharifying enzyme and water according to a mass ratio of 100: 1.5: 0.2: 1200, uniformly mixing, adjusting the pH to 4.5 by using 1mol/L hydrochloric acid aqueous solution, stirring for 20 minutes at the rotation speed of 150 rpm under the conditions that the microwave power is 400W, the microwave frequency is 2450MHz and the temperature is 50 ℃, heating to 98 ℃, and keeping the temperature for 10 minutes to inactivate enzyme to obtain reaction liquid A; filtering the reaction liquid A, then carrying out vacuum freeze drying, controlling the thickness of the material to be 6mm, setting the pre-freezing temperature to be-25 ℃, keeping for 2 hours after the temperature of the sample is reduced to the set temperature, setting the sublimation temperature to be 10 ℃, the resolution temperature to be 35 ℃, the vacuum degree to be 20pa, and the drying time to be 15 hours; obtaining activated sodium lignosulfonate; mixing activated sodium lignin sulfonate and an alcohol solution according to a mass ratio of 1: 10, pouring the mixture into a three-neck flask with a reflux condenser pipe and a thermometer, adjusting the pH to 10.5 by using 1mol/L aqueous solution of sodium hydroxide, adding 1-bromododecane accounting for 20 percent of the weight of the activated sodium lignosulfonate and pyridine accounting for 5 percent of the weight of the activated sodium lignosulfonate, carrying out condensation reflux reaction for 8 hours at 80 ℃ under the protection of nitrogen, and stopping the reaction to obtain reaction liquid B; washing the reaction liquid B with petroleum ether to remove unreacted 1-bromododecane, then carrying out vacuum freeze drying, controlling the thickness of the material to be 8mm, setting the pre-freezing temperature to be-25 ℃, keeping for 2 hours after the temperature of the sample is reduced to the set temperature, setting the sublimation temperature to be 15 ℃, the resolution temperature to be 35 ℃, the vacuum degree to be 15pa, and drying for 12 hours; obtaining alkylated sodium lignosulfonate; the alcohol solution is an ethanol water solution, and the mass concentration of the ethanol is 10%.
Example 11
The raw materials (weight portions) of a novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate are as follows: 790 parts of clopyralid, 33 parts of methylene dinaphthalene sodium sulfonate, 77 parts of sodium alkyl lignosulfonate, 50 parts of sodium dodecyl sulfate, 50 parts of ammonium sulfate and 2000 parts of water.
A preparation method of a novel low-toxicity cytoblast herbicide with high efficiency and high disintegration rate comprises the following steps:
s1, adding clopyralid, sodium methylene dinaphthalene sulfonate, sodium alkyl lignosulfonate, sodium dodecyl sulfate and ammonium sulfate into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 40MPa, the homogenizing temperature is 25 ℃, and the homogenizing time is 12 minutes; then shearing the mixture for 40 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2800 revolutions per part to obtain shearing emulsion; mixing the shearing emulsion and zirconia beads with the particle size of 0.6mm according to the mass ratio of 1: 1, adding the mixture into a sand mill for wet grinding, sampling at regular time every 30 minutes to determine the particle size until the particle size D90 of a suspension system is less than 5 mu m, and filtering by adopting 300-mesh filter cloth to obtain the water suspending agent;
s3, spray-drying the aqueous suspension agent by a spray dryer, wherein the air inlet temperature is 115 ℃, the air outlet temperature is 95 ℃, the sample injection speed is 700mL/h, and the hot air flow is 30m3The aperture of the nozzle is 0.7mm, and the novel low-toxicity cyto-herbicide with high efficiency and high disintegration rate is obtained. The suspension rate, the disintegration and the heat storage stability of the novel low-toxicity cytochalybeate herbicide with high efficiency and high disintegration rate are tested, and the test result is as follows: the thermal storage decomposition rate is 0.13%The suspension rate was 99.7%, and the disintegration time was 62 seconds.
The preparation process of the alkylated sodium lignosulfonate comprises the following steps: mixing sodium lignin sulfonate, laccase, saccharifying enzyme and water according to a mass ratio of 100: 1.5: 0.2: 1200, uniformly mixing, adjusting the pH to 4.5 by using 1mol/L hydrochloric acid aqueous solution, stirring for 20 minutes at the rotation speed of 150 rpm under the conditions that the microwave power is 400W, the microwave frequency is 2450MHz and the temperature is 50 ℃, heating to 98 ℃, and keeping the temperature for 10 minutes to inactivate enzyme to obtain reaction liquid A; filtering the reaction liquid A, then carrying out vacuum freeze drying, controlling the thickness of the material to be 6mm, setting the pre-freezing temperature to be-25 ℃, keeping for 2 hours after the temperature of the sample is reduced to the set temperature, setting the sublimation temperature to be 10 ℃, the resolution temperature to be 35 ℃, the vacuum degree to be 20pa, and the drying time to be 15 hours; obtaining activated sodium lignosulfonate; mixing activated sodium lignin sulfonate and an alcohol solution according to a mass ratio of 1: 10, pouring the mixture into a three-neck flask with a reflux condenser pipe and a thermometer, adjusting the pH to 10.5 by using 1mol/L aqueous solution of sodium hydroxide, adding 1-bromododecane accounting for 20 percent of the weight of the activated sodium lignosulfonate and pyridine accounting for 5 percent of the weight of the activated sodium lignosulfonate, carrying out condensation reflux reaction for 8 hours at 80 ℃ under the protection of nitrogen, and stopping the reaction to obtain reaction liquid B; washing the reaction liquid B with petroleum ether to remove unreacted 1-bromododecane, then carrying out vacuum freeze drying, controlling the thickness of the material to be 8mm, setting the pre-freezing temperature to be-25 ℃, keeping for 2 hours after the temperature of the sample is reduced to the set temperature, setting the sublimation temperature to be 15 ℃, the resolution temperature to be 35 ℃, the vacuum degree to be 15pa, and drying for 12 hours; obtaining alkylated sodium lignosulfonate; the alcohol solution is an ethanol water solution, and the mass concentration of the ethanol is 10%.
Test example 1
The novel low-toxicity cytometric herbicides with high efficiency and high disintegration rate prepared in examples 1 to 10 were tested for suspension rate, disintegration property and heat storage stability. Specific test data are shown in table 1.
Table 1: test data sheet
| Name of sample | A thermal storage decomposition rate% | Suspension rate% | Disintegration time, second |
| Example 1 | 0.30 | 98.3 | 81 |
| Example 2 | 0.95 | 94.1 | 106 |
| Example 3 | 0.61 | 96.8 | 155 |
| Example 4 | 1.74 | 91.5 | 97 |
| Example 5 | 5.88 | 88.7 | 139 |
| Example 6 | 0.69 | 90.4 | 118 |
| Example 7 | 0.73 | 93.5 | 101 |
| Example 8 | 0.66 | 92.6 | 114 |
| Example 9 | 0.82 | 95.9 | 108 |
| Example 10 | 0.27 | 99.1 | 75 |
The invention researches an auxiliary agent system of pesticide by single factor experiment. The optimal formula of the auxiliary agent of the dry suspending agent is obtained, and the dry suspending agent is further processed into the suspending agent according to the formula, so that the purposes of high disintegration rate, high efficiency, low toxicity and prolonged effective period are achieved.
Claims (2)
1. The cytometaherbicide is characterized by being prepared from the following raw materials in parts by weight: 810 parts of clopyralid, 120 parts of dispersion auxiliary agent for dry suspension, 40-60 parts of wetting auxiliary agent for dry suspension, 40-60 parts of disintegration auxiliary agent for dry suspension and 2500 parts of water 1500;
the wetting auxiliary agent special for dry suspension is sodium dodecyl sulfate;
the special disintegration auxiliary agent for dry suspension is ammonium sulfate;
the dispersing auxiliary agent special for dry suspension consists of 25-35wt% of methylene dinaphthalene sodium sulfonate and 65-75wt% of alkylated sodium lignin sulfonate;
the preparation process of the alkylated sodium lignosulfonate comprises the following steps: mixing sodium lignosulphonate, laccase, saccharifying enzyme and water according to the mass ratio of (95-105): (1-2): (0.1-0.3): (1100-1300), adjusting the pH to 4-5 with 0.8-1.2mol/L hydrochloric acid aqueous solution, stirring for 15-25 minutes at the rotation speed of 120-180 rpm under the conditions that the microwave power is 300-500W, the microwave frequency is 2400-2500MHz and the temperature is 45-55 ℃, and then heating to 90-100 ℃ for heat preservation for 8-12 minutes to inactivate the enzyme to obtain a reaction solution A; filtering the reaction solution A, and freeze-drying to obtain activated sodium lignosulfonate; mixing activated sodium lignin sulfonate and an alcohol solution according to a mass ratio of 1: (5-15) pouring the mixture into a three-neck flask with a reflux condenser pipe and a thermometer, adjusting the pH to 10-11 by using 0.8-1.2mol/L aqueous solution of sodium hydroxide, adding 1-bromododecane accounting for 15-25% of the weight of the activated sodium lignosulfonate and pyridine accounting for 3-7% of the weight of the activated sodium lignosulfonate, carrying out reflux condensation reaction for 5-10 hours at 75-85 ℃ under the protection of nitrogen, and stopping the reaction to obtain a reaction solution B; washing the reaction liquid B with petroleum ether to remove unreacted 1-bromododecane, and freeze-drying to obtain alkylated sodium lignosulfonate; wherein the alcoholic solution is an ethanol aqueous solution, and the mass concentration of the ethanol is 5-15%;
the dosage form of the cytometaherbicide is a dry suspending agent.
2. A method for preparing a cyto-herbicide according to claim 1, comprising the steps of:
s1, adding clopyralid, the dispersing aid special for dry suspension, the wetting aid special for dry suspension and the disintegrating aid special for dry suspension into water, and uniformly mixing to obtain slurry;
s2, homogenizing the slurry by a homogenizer, wherein the homogenizing pressure is 35-45MPa, the homogenizing temperature is 20-30 ℃, and the homogenizing time is 10-20 minutes; then shearing the mixture for 30 to 90 minutes by using a high-shear dispersion emulsifying machine at the rotating speed of 2500-; mixing the shearing emulsion and zirconia beads with the particle size of 0.5-0.7mm according to the mass ratio of 1: (0.8-1.2) adding the mixture into a sand mill for wet grinding, sampling and determining the particle size every 25-35 minutes until the particle size D90 of a suspension system is less than 5 mu m, and filtering to obtain the aqueous suspension;
s3, spray drying the water suspending agent, wherein the air inlet temperature is 110-3And/h, obtaining the cytoherbicide.
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| CN109575144B (en) * | 2018-12-03 | 2021-07-02 | 济南天邦化工有限公司 | Quaternary ammonium-sulfonated microcrystalline cellulose stabilizer and application thereof in cytometaherbicide |
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