CN107410296A - A kind of preparation method of pyraclostrobin and copper rosinate suspending agent - Google Patents
A kind of preparation method of pyraclostrobin and copper rosinate suspending agent Download PDFInfo
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- CN107410296A CN107410296A CN201710481762.1A CN201710481762A CN107410296A CN 107410296 A CN107410296 A CN 107410296A CN 201710481762 A CN201710481762 A CN 201710481762A CN 107410296 A CN107410296 A CN 107410296A
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- pyraclostrobin
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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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing carboxylic groups or thio analogues thereof, directly attached by the carbon atom to a cycloaliphatic ring; Derivatives thereof
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
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Abstract
The invention discloses a kind of preparation method containing pyraclostrobin and copper rosinate suspending agent, belong to agricultural bacteriocide technical field, this method uses the one-step synthesis copper rosinate in aqueous phase, and pyraclostrobin active compound is added in building-up process, then prepare pyraclostrobin and copper rosinate suspending agent by the way that technique is sanded.Suspending agent complex process different from the past, method of the invention one-step synthesis copper rosinate and can produce pyraclostrobin and copper rosinate suspending agent.The mass percent of institute's pyraclostrobin-containing and copper rosinate is 1 in the invention suspending agent：10~2：1, active ingredient (i.e. pyraclostrobin and copper rosinate) mass percent is 5%~40% in composition, and remaining is the auxiliary component and water needed for suspending agent preparation process.The compounding suspending agent of the invention is mainly used in agriculturally preventing and treating a variety of fungies and the bacterial disease of crop, while the growth to crop has obvious stimulation.
Description
Technical field
The present invention relates to a kind of preparation method of copper rosinate compounding suspending agent, and in particular to a kind of pyraclostrobin and pine
The preparation method of resin acid copper suspending agent, belongs to agricultural bacteriocide technical field.
Background technology
Pyraclostrobin is in the methoxy acrylic acid for having pyrrazole structure concurrently of exploitation in 1993 by BASF Aktiengesellschaft
Esters bactericide, by preventing electron transmission between thin race pigment b and C1 from being acted on to suppress mitochondrial respiratory, prevent mitochondria from producing
Energy (ATP) required for raw and offer cell eubolism, ultimately results in cell death.
Its structural formula is：
Physicochemical property：Pyraclostrobin white in appearance is to oldlace tasteless crystalline solid, fusing point:It is 63.7-65.2 DEG C, close
Degree：1.37 vapour pressure：2.6×10-8Pa(20-25℃)。
Pyraclostrobin wide sterilization spectrum, it can control Ascomycetes, Basidiomycetes, deuteromycetes, Oomycete etc. are most of to make
Thing fungal disease.Growth to spore germination and leaf intramatrical mycelium has very strong inhibitory action, has protection and therapeutic activity,
And there is stronger permeability and local absorbability, and lasting period length, resistance of rainwater washing against.It is widely used in preventing and treating wheat, rice, flower
Life, grape, vegetables, potato, banana, lemon, coffee, fruit tree, walnut, tealeaves, tobacco and ornamental plant, lawn and other are big
Multiple diseases on the crop of field.
Copper rosinate, also known as green newborn copper, chemical name 1,2,3,4,4a, 9,10,10a- octahydros-Isosorbide-5-Nitrae a- dimethyl -7-
(1- Methylethyls) -1- phenanthrene carboxylic acid copper, structural formula are：
Physicochemical property：Copper rosinate crystallizes for blue solid, fusing point：173~175 DEG C；Solubility (g/L, 20 DEG C)：
It is less than 1 in water, is soluble in the organic solvents such as toluene, acetone, DMF；PH5~7.
Copper rosinate is a kind of organic copper fungicide of high-efficiency low-toxicity wide spectrum, is had well to fungi, bacterial disease
Preventive and therapeutic action, to tens kinds of canker, epidemic disease, downy mildew, anthracnose, droop, leaf spot, root rot, rust etc.
Disease has good prevention effect, is a kind of new and effective wide-spectrum bactericide.Copper rosinate has very strong adherence and spread,
Resistance of rainwater washing against, and to the safe of crop and people and animals, do not produce poisoning, the characteristics of having the lasting period long, easy to use.Can
For preventing and treating the frequently seen plants disease caused by a variety of fungies and bacterium, while there is obvious stimulating growth to act on to vegetables.
Pyraclostrobin and copper rosinate compounding, it can be used for preventing and treating nearly all fungi and the bacterial disease of crop.
It simultaneously because both mechanism of action is different, can effectively delay the drug-fast generation of germ, and have to crop obvious
Stimulating growth acts on, and increases crop yield.
Through retrieval, it is 201110199917.5 to find number of patent application, and the content of the invention is " to contain pyraclostrobin and rosin
Sour copper fungicide complex composition " discloses the compounded combination on pyraclostrobin and copper rosinate bactericide, and the patent is public
It is missible oil, wettable powder, microemulsion, aqueous emulsion, aqueous suspension agent or water dispersible granules to have opened the possible formulation of this compounded combination.
But the preparation method disclosed in embodiment uses traditional formulations of pesticide preparation technology, that is, purchase copper rosinate active compound and pyrrole
Azoles kresoxim-methyl active compound, remixes the auxiliary agents such as dispersant, wetting agent, thickener, antifreezing agent, then carries out correlation by technique is sanded
The preparation of formulation, and among its disclosed missible oil, microemulsion, aqueous emulsion, a large amount of organic solvents are employed, not only producing
Process and using when have very big pollution to environment, and the increase of its cost in production can be caused, while increase it to make
Poisoning risk during to crops.
In actual development process, the inventors discovered that：Pyraclostrobin contains a variety of crystalline structures, wherein only a kind of brilliant
Type structure (fusing point is of a relatively high) is adapted to prepare suspending agent, and traditional handicraft will to the active compound structure and content of pyraclostrobin
Ask high, if the active compound selected is improper, easily occur livering phenomenon, and obtained suspending agent sample heat in sand grinding process
Often there are the quality problems such as condensate oil in storage, influences product using effect and sale.
Therefore it provides a kind of production technology is simplified, production cost reduces, while without waste water, waste residue, waste gas in production process
Discharge, realizes that the pyraclostrobin of the cleanly production of pesticidal preparations and the preparation method of copper rosinate suspending agent just turn into the skill
It is badly in need of the technical barrier solved in art field.
The content of the invention
It is an object of the invention to provide the preparation method of a kind of pyraclostrobin and copper rosinate suspending agent, this method is being closed
Into pyraclostrobin is added during copper rosinate, a step is made pyraclostrobin and copper rosinate suspending agent, simplifies life
Flow is produced, production cost is reduced, realizes cleanly production.
The purpose of the present invention is reached by following scheme：
A kind of preparation method of pyraclostrobin and copper rosinate suspending agent, its preparation process are as follows：
(1) preparation of aqueous slkali：Take a certain amount of alkali soluble in water, obtain aqueous slkali；
(2) preparation of saponification liquor：Rosin or modified rosin are added into aqueous slkali obtained by step (1), and is heated to 85
~95 DEG C, react 30~120 minutes, until reaction is complete, obtain saponification liquor；
(3) melting of pyraclostrobin：In the saponification liquor obtained by step (2), pyraclostrobin active compound is added, keeps temperature
Degree the dissolving of pyraclostrobin active compound, adds stabilizer, stirred 15~45 minutes, the pyrazoles ether bacterium that must stablize at 85~95 DEG C
Ester soap lye mixture；
(4) preparation of inorganic copper salt solution：A certain amount of inorganic mantoquita is soluble in water, obtain inorganic copper salt solution；
(5) preparation of copper rosinate：Added into pyraclostrobin mixing soap lye obtained by step (3) obtained by step (4)
Inorganic copper salt solution, 85~95 DEG C of keeping temperature, quick stirring, continue 40~150 minutes, obtain reaction product；
(6) dispersant is added in reactant mixture obtained by step (5), and stops heating, continue stirring more than 30 minutes,
Obtain reactant mixture；
(7) reactant mixture obtained by step (6) is ground after colloid mill pre-processes, then by sand mill, most
Thickener and antifreezing agent are added afterwards, then is ground, and produce pyraclostrobin and copper rosinate suspending agent.
A kind of optimal technical scheme, it is characterised in that：Alkali described in the step (1) is sodium hydroxide, potassium hydroxide,
The mixture of one or more of arbitrary proportions in monoethanolamine.
A kind of optimal technical scheme, it is characterised in that：Rosin described in the step (2) is gum rosin, wood rosin, gone
The mixture of one or more of arbitrary proportions in hydrogen rosin, Starex, maleic rosin, disproportionated rosin.
A kind of optimal technical scheme, it is characterised in that：Stabilizer described in the step (3) is polyvinyl alcohol, poly- second
The mixture of one or several kinds of arbitrary proportions in alkene pyrrolidone, chitosan or polyacrylic resin.
A kind of optimal technical scheme, it is characterised in that：Inorganic mantoquita described in the step (4) is copper sulphate, chlorination
The mixture of one or more of arbitrary proportions in copper or copper nitrate.
A kind of optimal technical scheme, it is characterised in that：Dispersant described in the step (5) contracts for alkylnaphthalene sulfonate
Polymers, naphthalene sulfonic acid-formaldehyde condensation product, polycarboxylic acid salt's dispersant, ethoxylated castor oil, phenethyl phenol polyoxyethylene polyoxy
The mixture of one or more of arbitrary proportions in propylene ether, castor oil polyoxyethylene ether or sodium lignin sulfonate.
A kind of optimal technical scheme, it is characterised in that：Described in alkali and the step (2) described in the step (1)
Rosin or modified rosin mass ratio be 1:2~1:10.
A kind of optimal technical scheme, it is characterised in that：Inorganic mantoquita and the step (2) described in the step (4)
Described in rosin or modified rosin mass ratio be 1:1~1:5.
A kind of optimal technical scheme, it is characterised in that：Pyraclostrobin and the step described in the step (3)
(2) mass ratio of rosin or modified rosin described in is 1:1~1:5.
Advantages of the present invention：
1. the characteristics of present invention utilizes pyraclostrobin low melting point, is added in copper rosinate building-up process, simplify
Production technology, reduces production cost, without any organic solvent, reduces environmental toxicity, while without useless in production process
The discharge of water, waste residue, waste gas, realize the cleaning chemical conversion production of pesticidal preparations.
2. pyraclostrobin of the present invention melts in the hot stage of production process so that the particle of pyraclostrobin is thinner more
Uniformly, simultaneously because dispersant, the scattered and package action of stabilizer, pyraclostrobin particle is more stable in formulation,
So that pyraclostrobin and copper rosinate suspending agent that the patented product is prepared than traditional handicraft have higher preparation stability
And effect.
Below by the drawings and specific embodiments, the present invention is described in detail.It should be understood that described reality
Apply example and only relate to the preferred embodiments of the invention, in the case of the spirit and scope of the present invention are not departed from, various composition and contain
The changes and improvements of amount are all possible.
Brief description of the drawings
The photo of the gained pyraclostrobin of the embodiment of the present invention 1 and copper rosinate suspending agent in Fig. 1.
The photo of the gained pyraclostrobin of comparative examples 1 and copper rosinate suspending agent of the present invention in Fig. 2.
The photo of the gained pyraclostrobin of the embodiment of the present invention 2 and copper rosinate suspending agent in Fig. 3.
The photo of the gained pyraclostrobin of comparative examples 2 and copper rosinate suspending agent of the present invention in Fig. 4.
The photo of the gained pyraclostrobin of the embodiment of the present invention 3 and copper rosinate suspending agent in Fig. 5.
The photo of the gained pyraclostrobin of comparative examples 3 and copper rosinate suspending agent of the present invention in Fig. 6.
Embodiment
Embodiment 1
A kind of preparation method of pyraclostrobin and copper rosinate suspending agent, its step are as follows：
(1) preparation of potassium hydroxide solution：Take 40Kg potassium hydroxide to be dissolved in 400Kg water, obtain potassium hydroxide solution；
(2) preparation of saponification liquor：210Kg rosin is added into potassium hydroxide solution obtained by step (1), and is heated to 90
DEG C, react 60 minutes, until reaction is complete, obtain saponification liquor；
(3) melting of pyraclostrobin：In the saponification liquor obtained by step (2), 20.5Kg pyraclostrobin active compounds are added
(crystal formation II, content 97.5%, 63.7-64.1 DEG C of fusing point), 90 DEG C are maintained the temperature at, pyraclostrobin active compound melts, and adds
Stabilizer 3Kg commercial polyethylene alcohol, stir 30 minutes, the pyraclostrobin soap lye mixture that must stablize；
(4) preparation of copper-bath：105Kg copper sulphate is dissolved in 150Kg hot water, obtains copper-bath；
(5) preparation of copper rosinate：Added into pyraclostrobin mixing soap lye obtained by step (3) obtained by step (4)
Copper-bath, 90~95 DEG C of keeping temperature, quick stirring, continue reaction 40 minutes, obtain reaction product；
(6) the commercially available castor oil polyoxyethylene ethers of 40Kg and the commercially available alkyl of 10Kg are added in reaction product obtained by step (5)
Naphthalene sulphonate, and stop heating, continue stirring 30 minutes, obtain reactant mixture；
(7) reactant mixture obtained by step (6) is ground after colloid mill pre-processes, then by sand mill, most
The commercially available xanthans of 1Kg and the commercially available ethylene glycol of 30Kg are added afterwards, then is ground, and adds water quantitative to 1000Kg, produce 2% pyrazoles ether bacterium
The copper rosinate suspending agent of ester 20%.
Comparative examples 1
By formula rate, by enough pyraclostrobin active compounds (crystal formation II, content 97.5%, 63.7-64.1 DEG C of fusing point)
It is wet through high speed shear with copper rosinate active compound (content 65%), wetting agent, dispersant, thickener, antifreezing agent etc. and water mixing
Method is sanded, and last homogeneous filter produces product.Capital equipment is batching kettle, colloid mill or homogeneous mixer, sand mill.
Formula：The commercially available pyraclostrobins of precise 20.5Kg (crystal formation II, content 97.5%, 63.7-64.1 DEG C of fusing point),
The commercially available copper rosinate active compounds (content 65%) of 307.7Kg；Dispersant is the commercially available castor oil polyoxyethylene ethers of 40Kg；Wetting agent is
The commercially available alkylnaphthalene sulfonate condensation polymers of 10Kg；Thickener is the commercially available xanthans of 1Kg；Antifreezing agent is the commercially available ethylene glycol of 30Kg；Carrier
For water, 1000Kg is complemented to, processing is ground to above-mentioned material by traditional handicraft, produces the pine of 2% pyraclostrobin 20%
Resin acid copper suspending agent.
The performance test results see the table below 1：
1st, micro- sem observation particle state distribution：With LIOO JS-500 binocular biological microscopes, in 10*40 enlargement ratios
Lower observation embodiment 1 and 1 suspending agent of comparative examples, 100 times of dilutions are simultaneously taken pictures, and respectively obtain photo as illustrated in fig. 1 and 2.
2nd, suspensibility (%)：Embodiment 1 and control are determined respectively with GB/T 14825-2006 agricultural-chemical suspension rate assay methods
The suspensibility of the dilution of embodiment 1.
Suspensibility intuitively illustrates suspended state of the active ingredient in water in decoction, and suspensibility height shows active ingredient
There is more preferable existence in water, can also obtain more preferable effect during use.By can be seen that in table 1：The dilution of embodiment 1
Liquid has higher suspensibility, illustrates that embodiment 1 has more preferable formulation advantage than comparative examples 1.
3rd, surface tension (mN/M) test of 500 times of dilutions：By embodiment 1 and the 2% pyrazoles ether of gained of comparative examples 1
500 times of the copper rosinate suspension dilution agent of bacterium ester 20%, it is tested with Shanghai full-automatic surface/interfacial tensimeters of BZY-1 of weighing and considering in order to uphold justice
Surface tension.
Surface tension, which refers to, acts on liquid surface, the power for reducing liquid surface area.In agricultural production application, table is commonly used
Face tension force represents that medicine drops in the complexity that crop surface is sprawled, and general upper surface tension value is smaller, then liquid it is easier
Crop surface contact is sprawled, and service efficiency is higher.As seen from Table 1：The dilution of embodiment 1 has lower surface tension
Value, illustrate that embodiment 1 has more preferable spread performance compared with the suspending agent of the gained of comparative examples 1.
Table 1
Embodiment 2
A kind of preparation method of pyraclostrobin and copper rosinate suspending agent, its step are as follows：
(1) preparation of potassium hydroxide solution：Take 20Kg sodium hydroxides to be dissolved in 400Kg water, obtain sodium hydroxide solution；
(2) preparation of saponification liquor：105Kg rosin is added into potassium hydroxide solution obtained by step (1), and is heated to 90
DEG C, react 60 minutes, until reaction is complete, obtain saponification liquor；
(3) melting of pyraclostrobin：In the saponification liquor obtained by step (2), 208.4Kg pyraclostrobin active compounds are added
(crystal formation I, content 96%, 64.6-65.2 DEG C of fusing point), 90 DEG C are maintained the temperature at, pyraclostrobin active compound melts, and adds stabilization
Agent 1Kg commercial polyethylene alcohol gathers and 2Kg commercial polypropylene acid resins, stirs 30 minutes, the pyraclostrobin soap lye that must stablize mixes
Compound；
(4) preparation of copper-bath：62.5Kg copper sulphate is dissolved in 150Kg hot water, obtains copper-bath；
(5) preparation of copper rosinate：Added into pyraclostrobin mixing soap lye obtained by step (3) obtained by step (4)
In copper-bath, 90~95 DEG C of keeping temperature, quick stirring, continue reaction 40 minutes, obtain reaction product；
(6) the commercially available alkylbenzene phenolic group phenol polyethenoxy ethers of 40Kg and 10Kg cities are added in reaction product obtained by step (5)
Alkylnaphthalene sulfonate condensation polymer is sold, and stops heating, continues stirring 30 minutes, obtains reactant mixture；
(7) reactant mixture obtained by step (6) is ground after colloid mill pre-processes, then by sand mill, most
The commercially available xanthans of 2Kg and the commercially available ethylene glycol of 30Kg are added afterwards, then is ground, and adds water quantitative to 1000Kg, produce 20% pyrazoles ether
The copper rosinate suspending agent of bacterium ester 10%.
Comparative examples 2
By formula rate, by enough pyraclostrobin active compounds (crystal formation I, content 96%, 64.6-65.2 DEG C of fusing point) and pine
Resin acid copper active compound (content 63%), wetting agent, dispersant, thickener, antifreezing agent etc. and water mixing, through high speed shear, wet method sand
Mill, last homogeneous filter produce product.Capital equipment is batching kettle, colloid mill or homogeneous mixer, sand mill.
Formula：The commercially available pyraclostrobins of precise 208.4Kg (crystal formation I, content 96%, 64.6-65.2 DEG C of fusing point),
158.7Kg commercially available copper rosinate active compound (content 63%)；Dispersant is the commercially available alkylbenzene phenolic group phenol polyethenoxy ethers of 40Kg；Wetting
Agent is that 10Kg sells alkylnaphthalene sulfonate condensation polymer；Thickener is the commercially available xanthans of 2Kg；Antifreezing agent is the commercially available ethylene glycol of 30Kg；Carry
Body is water, complements to 1000Kg, is ground processing to above-mentioned material by traditional handicraft, produces 20% pyraclostrobin 10%
Copper rosinate suspending agent.
The performance test results see the table below 2：
1st, micro- sem observation particle state distribution：With LIOO JS-500 binocular biological microscopes, in 10*40 enlargement ratios
Lower observation embodiment 2 and 2 suspending agent of comparative examples, 100 times of dilutions are simultaneously taken pictures, and respectively obtain photo as shown in Figures 3 and 4.
2nd, suspensibility (%)：Embodiment 2 and control are determined respectively with GB/T 14825-2006 agricultural-chemical suspension rate assay methods
The suspensibility of the dilution of embodiment 2.
Suspensibility intuitively illustrates suspended state of the active ingredient in water in decoction, and suspensibility height shows active ingredient
There is more preferable existence in water, can also obtain more preferable effect during use.By can be seen that in table 2：The dilution of embodiment 1
Liquid has higher suspensibility, illustrates that embodiment 2 has more preferable formulation advantage than comparative examples 2.
3rd, surface tension (mN/M) test of 500 times of dilutions：By embodiment 2 and 20% pyrazoles of gained of comparative examples 2
500 times of the copper rosinate suspension dilution agent of kresoxim-methyl 10%, tested with weigh and consider in order to uphold justice full-automatic surfaces of BZY-1/interfacial tensimeter of Shanghai
Its surface tension.
Surface tension, which refers to, acts on liquid surface, the power for reducing liquid surface area.In agricultural production application, table is commonly used
Face tension force represents that medicine drops in the complexity that crop surface is sprawled, and general upper surface tension value is smaller, then liquid it is easier
Crop surface contact is sprawled, and service efficiency is higher.As seen from Table 2：The dilution of embodiment 2 has lower surface tension
Value, illustrate that embodiment 2 has more preferable spread performance compared with the suspending agent of the gained of comparative examples 2.
4th, heat storage stability：By embodiment 2 and the copper rosinate of 20% pyraclostrobin 10% of the gained of comparative examples 2
Suspending agent is respectively put into 54 DEG C of ± 0.2 DEG C of constant temperature ovens, observes the heat storage stability of preparation.
After heat storage 2 weeks, the suspending agent of embodiment 2 is found, good fluidity, sticky and caking phenomenon does not occur, and dilute
After to enter water dispersible good；The suspending agent of comparative examples 2 is and irrecoverable then there occurs serious condensate oil and livering phenomenon.Say
The suspending agent of the bright gained of embodiment 2 has more preferable heat storage stability.
Table 2
Embodiment 3
A kind of preparation method of pyraclostrobin and copper rosinate suspending agent, its step are as follows：
(1) preparation of potassium hydroxide solution：Take 30Kg potassium hydroxide to be dissolved in 400Kg water, obtain potassium hydroxide solution；
(2) preparation of saponification liquor：160Kg rosin is added into potassium hydroxide solution obtained by step (1), and is heated to 90
DEG C, react 60 minutes, until reaction is complete, obtain saponification liquor；
(3) melting of pyraclostrobin：In the saponification liquor obtained by step (2), 31.1Kg pyraclostrobin active compounds are added
(crystal formation III, content 96.5%, 64.2-64.9 DEG C of fusing point), 90 DEG C are maintained the temperature at, pyraclostrobin active compound melts, and adds
Stabilizer, stir 30 minutes, the pyraclostrobin soap lye mixture that must stablize；
(4) preparation of copper-bath：80Kg copper sulphate is dissolved in 150Kg hot water, obtains copper-bath；
(5) preparation of copper rosinate：Added into pyraclostrobin mixing soap lye obtained by step (3) obtained by step (4)
Copper-bath, 90~95 DEG C of keeping temperature, quick stirring, continue reaction 40 minutes, obtain reaction product；
(6) the commercially available castor oil polyoxyethylene ethers of 40Kg are added in reaction product obtained by step (5) and 10Kg is commercially available wooden
Plain sodium sulfonate, and stop heating, continue stirring 30 minutes, obtain reactant mixture；
(7) reactant mixture obtained by step (6) is ground after colloid mill pre-processes, then by sand mill, most
The commercially available xanthans of 3Kg and the commercially available ethylene glycol of 30Kg are added afterwards, then is ground, and adds water quantitative to 1000Kg, produce 3% pyrazoles ether bacterium
The copper rosinate suspending agent of ester 15%.
Comparative examples 3
By formula rate, by enough pyraclostrobin active compounds(Crystal formation III, content 96.5%, 64.2-64.9 DEG C of fusing point)
It is wet through high speed shear with copper rosinate active compound (content 63%), wetting agent, dispersant, thickener, antifreezing agent etc. and water mixing
Method is sanded, and last homogeneous filter produces product.Capital equipment is batching kettle, colloid mill or homogeneous mixer, sand mill.
Formula：The commercially available pyraclostrobins of precise 31.1Kg (crystal formation III, content 96.5%, 64.2-64.9 DEG C of fusing point),
The commercially available copper rosinate active compounds (content 63%) of 238.1Kg；Dispersant is the commercially available castor oil polyoxyethylene ethers of 40Kg；Wetting agent is 10Kg
Commercially available sodium lignin sulfonate；Thickener is the commercially available xanthans of 3Kg；Antifreezing agent is the commercially available ethylene glycol of 30Kg；Carrier is water, is complemented to
1000Kg, processing is ground to above-mentioned material by traditional handicraft, produces the copper rosinate suspending agent of 3% pyraclostrobin 15%.
The performance test results see the table below 3：
1st, micro- sem observation particle state distribution：With LIOO JS-500 binocular biological microscopes, in 10*40 enlargement ratios
Lower observation embodiment 3 and 3 suspending agent of comparative examples, 100 times of dilutions are simultaneously taken pictures, and respectively obtain photo as illustrated in Figures 5 and 6.
2nd, suspensibility (%)：Embodiment 3 and control are determined respectively with GB/T 14825-2006 agricultural-chemical suspension rate assay methods
The suspensibility of the dilution of embodiment 3.
Suspensibility intuitively illustrates suspended state of the active ingredient in water in decoction, and suspensibility height shows active ingredient
There is more preferable existence in water, can also obtain more preferable effect during use.By can be seen that in table 3：The dilution of embodiment 3
Liquid has higher suspensibility, illustrates that embodiment 3 has more preferable formulation advantage than comparative examples 3.
3rd, surface tension (mN/M) test of 500 times of dilutions：By embodiment 3 and the 3% pyrazoles ether of gained of comparative examples 3
500 times of the copper rosinate suspension dilution agent of bacterium ester 15%, it is tested with Shanghai full-automatic surface/interfacial tensimeters of BZY-1 of weighing and considering in order to uphold justice
Surface tension.
Surface tension, which refers to, acts on liquid surface, the power for reducing liquid surface area.In agricultural production application, table is commonly used
Face tension force represents that medicine drops in the complexity that crop surface is sprawled, and general upper surface tension value is smaller, then liquid it is easier
Crop surface contact is sprawled, and service efficiency is higher.As seen from Table 3：The dilution of embodiment 3 has lower surface tension
Value, illustrate that embodiment 3 has more preferable spread performance compared with the suspending agent of the gained of comparative examples 3.
4th, heat storage stability：By embodiment 3 and the copper rosinate of 3% pyraclostrobin 15% of the gained of comparative examples 3
Suspending agent is respectively put into 54 DEG C of ± 0.2 DEG C of constant temperature ovens, observes the heat storage stability of preparation.
After heat storage 2 weeks, the suspending agent of embodiment 3 is found, good fluidity, sticky and caking phenomenon does not occur, and dilute
After to enter water dispersible good；The suspending agent of comparative examples 3 is and irrecoverable then there occurs serious condensate oil and livering phenomenon.Say
The suspending agent of the bright gained of embodiment 3 has more preferable heat storage stability.
Table 3
Application Example：
The gained copper rosinate suspending agent of 3% pyraclostrobin 15% of foregoing invention embodiment 3 is prepared with traditional handicraft
The gained 3% pyraclostrobin 15% copper rosinate suspending agent of comparative examples 3 be used for preventing and treating cucumber downy mildew, find this hair
Bright product prepares product compared with traditional handicraft has more preferable prevention effect on cucumber downy mildew.
Testing program and conclusion are as follows：
1. reagent agent
The copper rosinate suspending agent of 3% pyraclostrobin 15% obtained by the A inventions.
The copper rosinate suspending agent of 3% pyraclostrobin 15% obtained by B traditional handicrafts.
2. for studying thing and controlling object：
(1) for studying thing：Cucumber, kind Beijing-Tianjin 3；
(2) controlling object：Cucumber downy mildew.
3. test process
Experiment sets 4 processing altogether, is respectively：The invention gained copper rosinate suspending agent of 3% pyraclostrobin 15% is watered
750 times of dilution；The copper rosinate suspending agent of 3% pyraclostrobin 15% obtained by traditional handicraft is watered 750 times and 500 of dilution respectively
Times；Clear water control group, each processing separately set 4 repetitions.It is continuous to spray 2 times, second of spray after 7d is spaced, respectively at for the first time
7d and 14d investigation incidence after dispenser.
4. investigation method and result of calculation
4.1 investigation methods are per random 4 sampling surveys of cell, and every is investigated 2 plants, every plant of all blades of investigation.
Grade scale：
0 grade：Disease-free spot；
1 grade：Lesion area accounts for less than the 5% of whole leaf area；
3 grades：Lesion area accounts for the 6%~10% of whole leaf area；
5 grades：Lesion area accounts for the 11%~25% of whole leaf area；
7 grades：Lesion area accounts for the 26%~50% of whole leaf area；
9 grades：Lesion area accounts for more than the 50% of whole leaf area；
4.2 prevention effect calculation formula：
In formula：CK and Pt represents the disease index of blank district and chemicals treatment district respectively, and corner brace 0 and 1 represents respectively
Before dispenser and after dispenser.
4.3 experimental result
The copper rosinate suspending agent of 1 different process of form, 3% pyrazoles 15% prevents and treats cucumber downy mildew effect
4.4 conclusion (of pressure testing)
As seen from the above table, in the preventing and treating of cucumber downy mildew, 3% standby pyraclostrobin 15% of patent system of the present invention
Copper rosinate suspending agent has obvious excellent compared with the copper rosinate suspending agent of 3% pyraclostrobin 15% prepared by traditional handicraft
Gesture, effect when diluting 750 times slightly dilute 500 times of effect better than traditional handicraft, hence it is evident that when diluting 750 times higher than traditional handicraft
Preventive effect.Drug cost can be reduced in use, while reduces the usage amount of medicament, more ecological, environmental protective.
The mass percent of institute's pyraclostrobin-containing and copper rosinate is 1 in suspending agent of the present invention：10~2：1, composition
Middle active ingredient (i.e. pyraclostrobin and copper rosinate) mass percent is 5%~40%, and remaining is suspending agent preparation process
Needed for auxiliary component and water.The compounding suspending agent of the invention is mainly used in agriculturally preventing and treating a variety of fungies and bacterium of crop
Venereal disease does harm to, while the growth to crop has obvious stimulation.
The preparation method of pyraclostrobin and copper rosinate suspending agent of the present invention, select to add in copper rosinate building-up process
Add pyraclostrobin, solve pyraclostrobin low melting point and be not easy to prepare the difficult point of suspending agent, step production pyraclostrobin and
Copper rosinate suspending agent, production efficiency, and the discharge without waste water, waste residue, waste gas are substantially increased, realizes the clear of pesticidal preparations
Clean is into production；And pyraclostrobin and copper rosinate suspending agent prepared by the technique, refer in particle diameter, suspensibility, surface tension etc.
Put on, there is obvious advantage than traditional handicraft, using effect is more secure.
It is described above, only it is highly preferred embodiment of the present invention and control case study on implementation, other forms not is made to the present invention
Limitation, any those skilled in the art are changed or are modified as equivalent change using the technology contents of the disclosure above
The equivalent embodiment of change.In every case it is without departing from technical solution of the present invention content, the technical spirit according to the present invention is implemented to more than
Any modification, equivalent variations and the remodeling that example is made, still fall within the protection domain of technical solution of the present invention.
Claims (9)
1. the preparation method of a kind of pyraclostrobin and copper rosinate suspending agent, its step is as follows：
(1) preparation of aqueous slkali：Take a certain amount of alkali soluble in water, obtain aqueous slkali；
(2) preparation of saponification liquor：Rosin or modified rosin are added into aqueous slkali obtained by step (1), and is heated to 85~95
DEG C, react 30~120 minutes, until reaction is complete, obtain saponification liquor；
(3) melting of pyraclostrobin：In the saponification liquor obtained by step (2), pyraclostrobin active compound is added, is maintained the temperature at
85~95 DEG C, the dissolving of pyraclostrobin active compound, stabilizer is added, is stirred 15~45 minutes, the pyraclostrobin soap that must stablize
Liquid mixture；
(4) preparation of inorganic copper salt solution：A certain amount of inorganic mantoquita is soluble in water, obtain inorganic copper salt solution；
(5) preparation of copper rosinate：Added into pyraclostrobin mixing soap lye obtained by step (3) inorganic obtained by step (4)
Copper salt solution, 85~95 DEG C of keeping temperature, quick stirring, continue 40~150 minutes, obtain reaction product；
(6) dispersant is added in reaction product obtained by step (5), and stops heating, continued stirring more than 30 minutes, must react
Mixture；
(7) reactant mixture obtained by step (6) is ground after colloid mill pre-processes, then by sand mill, finally added
Enter thickener and antifreezing agent, then grind, produce pyraclostrobin and copper rosinate suspending agent.
2. the preparation method of pyraclostrobin as claimed in claim 1 and copper rosinate suspending agent, it is characterised in that：The step
Suddenly the alkali described in (1) is the mixture that one or more of arbitrary proportions are obtained in sodium hydroxide, potassium hydroxide, monoethanolamine.
3. the preparation method of pyraclostrobin as claimed in claim 2 and copper rosinate suspending agent, it is characterised in that：The step
(2) rosin described in is gum rosin, wood rosin, dehydrogenation rosin, Starex, maleic rosin, one kind in disproportionated rosin or
The mixture of several arbitrary proportions.
4. the preparation method of pyraclostrobin as claimed in claim 3 and copper rosinate suspending agent, it is characterised in that：The step
Suddenly the stabilizer described in (3) be polyvinyl alcohol, polyvinylpyrrolidone, chitosan or polyacrylic resin in one kind or
The mixture of several arbitrary proportions.
5. the preparation method of pyraclostrobin as claimed in claim 4 and copper rosinate suspending agent, it is characterised in that：The step
Suddenly the inorganic mantoquita described in (4) is the mixture of one or more of arbitrary proportions in copper sulphate, copper chloride or copper nitrate.
6. the preparation method of pyraclostrobin as claimed in claim 5 and copper rosinate suspending agent, it is characterised in that：The step
Suddenly the dispersant described in (5) is alkylnaphthalene sulfonate condensation polymer, naphthalene sulfonic acid-formaldehyde condensation product, polycarboxylic acid salt's dispersant, second
In epoxide castor oil, phenethyl phenol polyoxyethylene poly-oxygen propylene aether, castor oil polyoxyethylene ether or sodium lignin sulfonate
The mixture of one or more of arbitrary proportions.
7. the preparation method of pyraclostrobin as claimed in claim 1 and copper rosinate suspending agent, it is characterised in that：The step
Suddenly the alkali described in (1) and the rosin described in the step (2) or the mass ratio of modified rosin are 1:2~1:10.
8. the preparation method of pyraclostrobin as claimed in claim 1 and copper rosinate suspending agent, it is characterised in that：The step
Suddenly the inorganic mantoquita described in (4) and the rosin described in step (2) or the mass ratio of modified rosin are 1:1~1:5.
9. the preparation method of pyraclostrobin as claimed in claim 1 and copper rosinate suspending agent, it is characterised in that：The step
Suddenly the pyraclostrobin described in (3) and the rosin described in the step (2) or the mass ratio of modified rosin are 1:1~1:5.
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| CN108184881A (en) * | 2017-12-28 | 2018-06-22 | 柳州市惠农化工有限公司 | A kind of missible oil containing copper rosinate and pyraclostrobin, preparation method and applications |
| CN114423286A (en) * | 2019-09-16 | 2022-04-29 | 伊士曼化工公司 | Agrochemical formulations containing sulfopolymers |
| EP4030904A4 (en) * | 2019-09-16 | 2023-09-27 | Eastman Chemical Company | Sticker formulation containing a sulfopolymer |
| EP4030913A4 (en) * | 2019-09-16 | 2023-09-27 | Eastman Chemical Company | Spreader formulation containing a sulfopolymer |
| EP4030912A4 (en) * | 2019-09-16 | 2023-09-27 | Eastman Chemical Company | Water immiscible solvent-in-water emulsion formulation containing a sulfopolymer |
| EP4030910A4 (en) * | 2019-09-16 | 2023-09-27 | Eastman Chemical Company | Rapid dispersal formulation containing a sulfopolymer |
| EP4030905A4 (en) * | 2019-09-16 | 2023-10-04 | Eastman Chemical Company | Agricultural inert package formulation containing a sulfopolymer |
| EP4030908A4 (en) * | 2019-09-16 | 2023-10-04 | Eastman Chemical Company | Substantially non-phytotoxic formulation containing a sulfopolymer |
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| CN103497101A (en) * | 2013-10-11 | 2014-01-08 | 广东植物龙生物技术有限公司 | Preparation method and application of resin acid copper salt synthesized by aqueous phase process |
| CN103493805A (en) * | 2013-10-11 | 2014-01-08 | 广东植物龙生物技术有限公司 | Copper rosinate suspending agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108184881A (en) * | 2017-12-28 | 2018-06-22 | 柳州市惠农化工有限公司 | A kind of missible oil containing copper rosinate and pyraclostrobin, preparation method and applications |
| CN114423286A (en) * | 2019-09-16 | 2022-04-29 | 伊士曼化工公司 | Agrochemical formulations containing sulfopolymers |
| EP4030904A4 (en) * | 2019-09-16 | 2023-09-27 | Eastman Chemical Company | Sticker formulation containing a sulfopolymer |
| EP4030913A4 (en) * | 2019-09-16 | 2023-09-27 | Eastman Chemical Company | Spreader formulation containing a sulfopolymer |
| EP4030912A4 (en) * | 2019-09-16 | 2023-09-27 | Eastman Chemical Company | Water immiscible solvent-in-water emulsion formulation containing a sulfopolymer |
| EP4030910A4 (en) * | 2019-09-16 | 2023-09-27 | Eastman Chemical Company | Rapid dispersal formulation containing a sulfopolymer |
| EP4030906A4 (en) * | 2019-09-16 | 2023-09-27 | Eastman Chemical Company | Agrochemical formulation containing a sulfopolymer |
| EP4030905A4 (en) * | 2019-09-16 | 2023-10-04 | Eastman Chemical Company | Agricultural inert package formulation containing a sulfopolymer |
| EP4030908A4 (en) * | 2019-09-16 | 2023-10-04 | Eastman Chemical Company | Substantially non-phytotoxic formulation containing a sulfopolymer |
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Application publication date: 20171201 |