CN109997845A - A kind of dispersible type agricultural chemicals suspension agent and preparation method thereof - Google Patents
A kind of dispersible type agricultural chemicals suspension agent 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
- 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
- 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
- A01N25/08—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 solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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- Chemical Kinetics & Catalysis (AREA)
- Pest Control & Pesticides (AREA)
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Abstract
The invention discloses a kind of dispersible type agricultural chemicals suspension agents and preparation method thereof, belong to insecticides adjuvant field.Viscosity reduction additive prepared by the present invention, so that pesticide dispersion mobility increases, suspending agent can carry out rapidly contact suspension after entering pesticide with pesticide, improve suspending agent activity；The dispersion activating agent of preparation, form one layer of polymeric adsorption layer, it prevents the close of pesticide granules and reunites, improve suspended dispersed performance, reduce moisture investment, on the other hand pesticide granules are wound using introducing branching arm, so that playing a supporting role between particle and particle, there is preferable stability after dispersion；Suspension thickener is added, so that the tackifying ability enhancing after suspending, improves the drug effect of pesticide, and is added a part of molten adjuvant of oil, improves automatic emulsifying performance, plays solubilizing effect, improve compatibility between component, so that suspending agent effect enhances.It is poor that the present invention solves current agricultural chemicals suspension agent suspension stability, the high problem of moisture.
Description
Technical field
The invention belongs to insecticides adjuvant technical field, it is related to a kind of dispersible type agricultural chemicals suspension agent and preparation method thereof.
Background technique
Insecticides adjuvant is the general name in chemical pesticide processing dosage form to various adjuvants used except effective component.It helps
Agent itself is indispensable additive without bioactivity, but in form formula or in application, adds the main mesh of auxiliary agent
Be to improve drug effect, reduce the dosage of pesticide, save the cost, reduce pollution of the pesticide to environment.Auxiliary agent especially removes pesticide
The synergistic effect of careless agent is mainly to pass through increase pesticide to ask and improve to plant table when the hold-up of plant surface, extension are detained
The penetration capacity of skin.Because the type of auxiliary agent is different, the mechanism of action is also different.In use, with tables such as emulsifier, profit spreaders
Face activating agent be it is more, purposes is wider, on powder performance influence it is also larger.The addition of surfactant, greatly reduces solution
Surface tension makes the droplet surface of medicament emulsion form one layer of strong protective film, enhances medicament in plant surface or pest
Wetting, spread and the adhesive force of body surface, to improve drug effect.Oil-suspending agent (Oil miscible flowable
Concentrate(oil miscible suspension), abbreviation OF), refer to the liquid system of the suspension of stable effective ingredients
Agent uses after being deployed with organic solvent diluting.Dispersible oil-suspending agent (OD) refers to one or more kinds of pesticide active ingredients
(wherein at least one is solid raw medicine) forms high dispersive, stable suspension system in non-water system decentralized medium, dilute with water
It is used after releasing.Vegetable oil type suspending agent is with vegetable oil such as soybean oil, rapeseed oil, cottonseed oil etc. for carrier, by the way that powder is sanded
It is broken, so that effective component is formed suspension in oily phase.Compared with other dosage forms, the oil in system is very strong to some lipophilicities
Pesticide, especially insoluble herbicide can play synergistic effect in the oil.Since the nineties in last century, the dosage form is increasingly
By the favor of wide farmers, pesticide producer also divides a point registration production, and it is rapid for especially developing in recent years excellent.It can for processing
There are many oil for dispersing oil-suspending agent, and one of the most common is soybean oil, methyl esters oil.Because of the wide model in soybean oil source, quality is stablized,
And it is good in crop surface plate-out ability, synergy is obvious, therefore general using the more of soybean oil.But the more difficult emulsification of soybean oil, pesticide
Enterprise and auxiliary agent producer are all the time all without selecting preferable emulsifying dispersant, and comparatively methyl esters oil is just easier cream
Change, therefore, producer major part portion produces dispersible oil-suspending agent with methyl esters oil.But it is used to produce the oleic acid or fat of methyl esters oil
The methyl esters oil quality of sour source too complex, different manufacturers or even same producer's different batches has very big difference, to lead
The quality fluctuation for causing final products that oil-suspending agent can be dispersed is very big.Also, client is when purchasing dispersible oil-suspending agent, generally all
It is the dispersible oil-suspending agent of soybean oil systems that requirement, which can be specified, therefore it is dispersible oil that oil-suspending agent, which can be dispersed, in soybean oil systems
The developing direction of suspending agent, researching and developing a kind of preferable soybean oil systems and oil-suspending agent auxiliary agent can be dispersed is to prepare soybean oil
The top priority of oil-suspending agent can be dispersed in system.The dispersible oil-suspending agent hydroxyl value of soybean oil systems is low currently on the market, moisture
High, pH value and lotion all produce unstability, are not able to satisfy the demand of people.
Summary of the invention
The technical problems to be solved by the invention:, moisture high problem poor for current agricultural chemicals suspension agent suspension stability,
A kind of dispersible type agricultural chemicals suspension agent and preparation method thereof is provided.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of dispersible type agricultural chemicals suspension agent, including viscosity reduction additive, dispersion activating agent, suspension thickener, the molten adjuvant of oil；
The viscosity reduction additive the preparation method comprises the following steps: taking 2- acrylamide-2-methyl propane sulfonic 2 ~ 5:2 in mass ratio ~ 6:10 ~ 20
Addition acrylic acid, deionized water are stirred, and obtain mixed liquor a, take initiator 1 ~ 3:0.5 in mass ratio ~ 0.8:10 ~ 15 to be added sub-
Sodium bisulfate, deionized water are stirred, and obtain mixed liquor b, and 1 ~ 5:10 ~ 30 in mass ratio mixed liquor b is taken to be added dropwise to mixed liquor a
In, it is passed through nitrogen protection, is stirred, stirring mixture is obtained, takes stirring mixture 2 ~ 6:10 in mass ratio ~ 15 that acetic acid second is added
Ester is stood, and takes precipitating dry to get viscosity reduction additive.
The initiator are as follows: take potassium peroxydisulfate 2 ~ 5:1 in mass ratio ~ 3 be added ammonium persulfate mixing to get.
It is described dispersion activating agent the preparation method comprises the following steps:
S1. it takes support dispersing matrixes object 4 ~ 9:5 in mass ratio ~ 10 that ethylene bromohyrin is added, adds support dispersing matrixes amount of substance
0.4 ~ 0.9% p-methyl benzenesulfonic acid, is passed through nitrogen protection, is stirred, and vacuum distillation must be evaporated under reduced pressure object a, take vacuum distillation
Acrylic acid, distilled water is added in object a 3 ~ 8:1 in mass ratio ~ 3:10 ~ 15, obtains mixture a, take mixture a 20 ~ 30:1 in mass ratio ~
5 are added 2,2- bipyridyl, adjust pH to 8 ~ 9, add the copper bromide of mixture a mass 1 ~ 5%, cooling in liquid nitrogen, thaw,
It is kept the temperature then at 80 ~ 90 DEG C, obtains mixture b；
S2. it takes mixture b 5 ~ 10:2 in mass ratio ~ 5:10 ~ 20 that allyl polyglycol methyl ether, water is added, adds mixing
2, the 2- bipyridyl of object b mass 5 ~ 10% adjusts pH to 5 ~ 6, cooling through liquid nitrogen, thaws, obtains mixture c, take mixture c by matter
Amount is added copper bromide than 10 ~ 20:1 ~ 3 and is stirred, and filters, filtrate is taken to disperse activating agent to obtain the final product.
In the step S1 support dispersing matrixes object the preparation method comprises the following steps:
(1) take acid additive 1 ~ 3:2 in mass ratio ~ 5:10 ~ 15 that N is added, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, solvent stir
Mixing is mixed, the boron trifluoride ether for adding acid additive quality 2 ~ 5% is stirred, and vacuum distillation obtains vacuum distillation object；
(2) it takes and is evaporated under reduced pressure object 2 ~ 5:1 in mass ratio ~ addition N of 3:10 ~ 15, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, toluene,
Mixture is obtained, the p-methyl benzenesulfonic acid of mixture quality 1 ~ 4% is added, is passed through nitrogen protection, is stirred, is evaporated under reduced pressure to get branch
Support dispersing matrixes object.
Acid additive in the step (1) are as follows: take tartaric acid 5 ~ 10:2 in mass ratio ~ 7 that lauric acid mixing is added, i.e.,
?.
Solvent in the step (1) are as follows: take toluene 10 ~ 20:3 in mass ratio ~ 5 that N,N-dimethylformamide is added mixed
Close to get.
The suspension thickener are as follows: take xanthan gum 3 ~ 5:1 in mass ratio ~ 3:10 ~ 20 that pulullan polysaccharide, aluminum magnesium silicate is added
Mixing to get.
The molten adjuvant of oil are as follows: take Crodaret 2 ~ 5:2 in mass ratio ~ 5:5 ~ 10 that polyoxyethylene is added
Castor oil, polyethylene glycol-400 mixing to get.
The preparation method includes the following steps:
A. according to the mass fraction, 3 ~ 6 parts of viscosity reduction additives, 1 ~ 3 part of n-octyl amine, 1 ~ 3 part of dicyclohexylcarbodiimide, 40 ~ 50 are taken
Part N-Methyl pyrrolidone is stirred, and is kept the temperature then at 55 ~ 65 DEG C, is stood in 1 ~ 4 DEG C, is filtered, take smoke filtrate in mass ratio 1 ~
3:5 ~ 15 is added sodium hydroxide solution and is stirred, and filters, filter residue is taken to wash through methanol, dry, obtains dried object；
B. according to the mass fraction, take 5 ~ 10 parts of dried objects, 10 ~ 20 parts of dispersion activating agents, 3 ~ 6 parts of suspension thickeners, 2 ~ 5 parts of oil molten
Adjuvant, 40 ~ 50 parts of water are stirred, and adjust pH to 7 ~ 7.2 to get dispersible type agricultural chemicals suspension agent.
The present invention is compared with other methods, and advantageous effects are:
(1) viscosity reduction additive prepared by the present invention be using 2- acrylamide-2-methyl propane sulfonic, acrylic acid as raw material in water into
Row free radical polymerization adds initiator and chain-transferring agent, forms copolymer, is eventually adding n-octyl amine as matrix and carries out amine
Change reaction to obtain, introduce alkyl side chain and form the substance for improving mobility with viscosity reduction of combed, utilizes hydrophobic side chain
It is contacted by drop low-surface-energy with pesticide drop, carries out oil-in-water and form moisture film in droplet surface, between raising drop
Greasy property, and pesticide dispersion mobility is increased, suspending agent can carry out rapidly contact suspension after entering pesticide with pesticide, mention
Higher suspension agent activity；
(2) dispersion activating agent prepared by the present invention is first to support dispersing matrixes object as base-material, is with tartaric acid, N, N- dihydroxy
Ethyl -3- amidos propionic acid methyl esters forms dissaving polymer, is re-introduced into a N, N- dihydroxy ethyl -3- amine by esterification
Base methyl propionate forms branching type polymer, and generates centronucleus dissaving polymer by ester exchange reaction with ethylene bromohyrin,
It is eventually adding acrylic acid, allyl polyglycol methyl ether is polymerize, substance of the formation with hyper-branched structure, molecule master
Chain is connected with carbon-carbon bond, and introducing on molecular backbone has the adsorption groups such as hydrophilic carboxyl and ether, can be adsorbed on pesticide
Particle surface forms one layer of polymeric adsorption layer, while logical long chain branch provides steric hindrance, prevent the close of pesticide granules and
Reunite, improve suspended dispersed performance, reduce moisture investment, on the other hand pesticide granules are wound using introducing branching arm,
So that playing a supporting role between particle and particle, there is preferable stability after dispersion；
(3) suspension thickener is added in the present invention, and it is anti-shearing to improve the flowing in dispersion process using xanthan gum, pulullan polysaccharide etc.
Ability improves so that the tackifying ability enhancing after suspending, improves the drug effect of pesticide, and is added a part of molten adjuvant of oil from cream
Change performance, play solubilizing effect, improve compatibility between component, so that suspending agent effect enhances；
(4) present invention first wraps up pesticide drop with viscosity reduction additive, forms moisture film, improves greasy property, then with dispersion
Activating agent is adsorbed and is provided steric hindrance, prevents from reuniting, and carries out diminishing, and carry out to pesticide granules using branching arm is introduced
Winding improves the stability of dispersion so that playing a supporting role between particle and particle, introduces suspension thickener and improves flowing shearing resistance
Shear force and tackifying ability enhance pesticide efficacy, most increase dissolubility and compatibility through the molten adjuvant of oil afterwards, coordinate between each component
Effect improves suspending agent effect.
Specific embodiment
Initiator are as follows: take potassium peroxydisulfate 2 ~ 5:1 in mass ratio ~ 3 be added ammonium persulfate mixing to get.
Viscosity reduction additive the preparation method comprises the following steps: taking 2- acrylamide-2-methyl propane sulfonic 2 ~ 5:2 in mass ratio ~ 6:10 ~ 20
Acrylic acid, deionized water is added, is stirred 20 ~ 30min, obtains mixed liquor a, take initiator 1 ~ 3:0.5 in mass ratio ~ 0.8:10
~ 15 are added sodium hydrogensulfite, deionized water, are stirred 10 ~ 20min, obtain mixed liquor b, take mixed liquor b 1 ~ 5:10 in mass ratio
~ 30 are added dropwise in mixed liquor a, are passed through nitrogen protection, are stirred 60 ~ 90min in 75 ~ 85 DEG C, obtain stirring mixture, take stirring
Ethyl acetate is added in mixture 2 ~ 6:10 in mass ratio ~ 15, stands 30 ~ 50min, takes precipitating dry to get viscosity reduction additive.
Solvent are as follows: take toluene 10 ~ 20:3 in mass ratio ~ 5 be added n,N-Dimethylformamide mixing to get.
Acid additive are as follows: take tartaric acid 5 ~ 10:2 in mass ratio ~ 7 be added lauric acid mixing to get.
Support dispersing matrixes object the preparation method comprises the following steps:
(1) acid additive 1 ~ 3:2 in mass ratio ~ 5:10 ~ 15 is taken to be added N, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, solvent, in
50 ~ 60 DEG C are stirred 20 ~ 30min, add the boron trifluoride ether of acid additive quality 2 ~ 5%, mixed in 90 ~ 100 DEG C of stirrings
4 ~ 7h is closed, vacuum distillation obtains vacuum distillation object；
(2) it takes and is evaporated under reduced pressure object 2 ~ 5:1 in mass ratio ~ addition N of 3:10 ~ 15, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, toluene,
Mixture is obtained, the p-methyl benzenesulfonic acid of mixture quality 1 ~ 4% is added, is passed through nitrogen protection, is stirred 2 ~ 5h in 110 ~ 120 DEG C,
Vacuum distillation is to get support dispersing matrixes object.
Disperse activating agent the preparation method comprises the following steps:
S1. it takes support dispersing matrixes object 4 ~ 9:5 in mass ratio ~ 10 that ethylene bromohyrin is added, adds support dispersing matrixes amount of substance
0.4 ~ 0.9% p-methyl benzenesulfonic acid, is passed through nitrogen protection, is stirred 5 ~ 7h in 100 ~ 110 DEG C, and vacuum distillation must be evaporated under reduced pressure
Object a takes vacuum distillation object a 3 ~ 8:1 in mass ratio ~ 3:10 ~ 15 that acrylic acid, distilled water is added, obtains mixture a, take mixture a by
2,2- bipyridyl is added in 20 ~ 30:1 of mass ratio ~ 5, adjusts pH to 8 ~ 9, the copper bromide of mixture a mass 1 ~ 5% is added, in liquid
It is cooling in nitrogen, it thaws, then at 80 ~ 90 DEG C of heat preservations 18 ~ for 24 hours, obtains mixture b；
S2. it takes mixture b 5 ~ 10:2 in mass ratio ~ 5:10 ~ 20 that allyl polyglycol methyl ether, water is added, adds mixing
2, the 2- bipyridyl of object b mass 5 ~ 10% adjusts pH to 5 ~ 6, cooling through liquid nitrogen, thaws, obtains mixture c, take mixture c by matter
Copper bromide is added than 10 ~ 20:1 ~ 3 in amount, and 10 ~ 15h is stirred in 20 ~ 25 DEG C, is filtered through alumina chromatographic column, takes filtrate to obtain the final product
Disperse activating agent.
Suspension thickener are as follows: take xanthan gum 3 ~ 5:1 in mass ratio ~ 3:10 ~ 20 that pulullan polysaccharide, aluminum magnesium silicate is added mixed
Close to get.
The molten adjuvant of oil are as follows: take Crodaret 2 ~ 5:2 in mass ratio ~ 5:5 ~ 10 that polyoxyethylene caster is added
Oil, polyethylene glycol-400 mixing to get.
A kind of preparation method of dispersible type agricultural chemicals suspension agent, includes the following steps:
A. according to the mass fraction, 3 ~ 6 parts of viscosity reduction additives, 1 ~ 3 part of n-octyl amine, 1 ~ 3 part of dicyclohexylcarbodiimide, 40 ~ 50 are taken
Part N-Methyl pyrrolidone, is stirred 1 ~ 3h in 500r/min, 50 ~ 60 DEG C, then at 55 ~ 65 DEG C of heat preservations 18 ~ for 24 hours, in 1 ~ 4 DEG C
3 ~ 5h is stood, is filtered, takes smoke filtrate 1 ~ 3:5 in mass ratio ~ 15 that the sodium hydroxide solution that mass fraction is 40% is added, stirring is mixed
60 ~ 90min is closed, filtering takes filter residue to wash through methanol, and it is dry, obtain dried object；
B. according to the mass fraction, take 5 ~ 10 parts of dried objects, 10 ~ 20 parts of dispersion activating agents, 3 ~ 6 parts of suspension thickeners, 2 ~ 5 parts of oil molten
Adjuvant, 40 ~ 50 parts of water are stirred 30 ~ 60min in 40 ~ 50 DEG C, adjust pH to 7 ~ 7.2 to get dispersible type agricultural-chemical suspension
Agent.
Embodiment 1
Initiator are as follows: take potassium peroxydisulfate 2:1 in mass ratio be added ammonium persulfate mixing to get.
Viscosity reduction additive the preparation method comprises the following steps: take 2- acrylamide-2-methyl propane sulfonic 2:2:10 in mass ratio be added third
Olefin(e) acid, deionized water, are stirred 20min, obtain mixed liquor a, take initiator 1:0.5:10 in mass ratio be added sodium hydrogensulfite,
Deionized water is stirred 10min, obtains mixed liquor b, takes mixed liquor b 1:10 to be in mass ratio added dropwise in mixed liquor a, is passed through nitrogen
Gas shielded is stirred 60min in 75 DEG C, obtains stirring mixture, takes stirring mixture 2:10 in mass ratio that ethyl acetate is added,
30min is stood, takes precipitating dry to get viscosity reduction additive.
Solvent are as follows: take toluene 10:3 in mass ratio be added n,N-Dimethylformamide mixing to get.
Acid additive are as follows: take tartaric acid 5:2 in mass ratio be added lauric acid mixing to get.
Support dispersing matrixes object the preparation method comprises the following steps:
(1) take acid additive 1:2:10 in mass ratio that N is added, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, solvent are stirred in 50 DEG C
Mixing 20min is mixed, the boron trifluoride ether of acid additive quality 2% is added, is stirred 4h in 90 DEG C, is evaporated under reduced pressure, must subtract
Press distillation；
(2) take vacuum distillation object 2:1:10 in mass ratio that N is added, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, toluene must mix
Object is added the p-methyl benzenesulfonic acid of mixture quality 1%, is passed through nitrogen protection, is stirred 2h in 110 DEG C, vacuum distillation to get
Support dispersing matrixes object.
Disperse activating agent the preparation method comprises the following steps:
S1. it takes support dispersing matrixes object 4:5 in mass ratio that ethylene bromohyrin is added, adds support dispersing matrixes amount of substance 0.4%
P-methyl benzenesulfonic acid is passed through nitrogen protection, is stirred 5h in 100 DEG C, and vacuum distillation must be evaporated under reduced pressure object a, take vacuum distillation object
Acrylic acid, distilled water is added in a 3:1:10 in mass ratio, obtains mixture a, takes mixture a 20:1 in mass ratio that 2,2- connection pyrrole is added
Pyridine adjusts pH to 8, adds the copper bromide of mixture a mass 1%, cooling in liquid nitrogen, thaws, then at 80 DEG C of heat preservation 18h, obtains
Mixture b；
S2. it takes mixture b 5:2:10 in mass ratio that allyl polyglycol methyl ether, water is added, adds mixture b mass 5%
2,2- bipyridyl, adjust pH to 5, it is cooling through liquid nitrogen, thaw, obtain mixture c, take mixture c 10:1 in mass ratio that bromine is added
Change copper, is stirred 10h in 20 DEG C, is filtered through alumina chromatographic column, filtrate is taken to disperse activating agent to obtain the final product.
Suspension thickener are as follows: take xanthan gum 3:1:10 in mass ratio be added pulullan polysaccharide, aluminum magnesium silicate mixing to get.
The molten adjuvant of oil are as follows: take Crodaret 2:2:5 in mass ratio that Emulsifier EL-60, poly- second is added
Glycol -400 mixing to get.
A kind of preparation method of dispersible type agricultural chemicals suspension agent, includes the following steps:
A. according to the mass fraction, 3 parts of viscosity reduction additives, 1 part of n-octyl amine, 1 part of dicyclohexylcarbodiimide, 40 parts of N- methyl pyrroles are taken
Pyrrolidone is stirred 1h in 500r/min, 50 DEG C, then at 55 DEG C of heat preservation 18h, in 1 DEG C of standing 3h, filters, take smoke filtrate by
The sodium hydroxide solution that mass fraction is 40% is added in mass ratio 1:5, is stirred 60min, filters, filter residue is taken to wash through methanol,
It is dry, obtain dried object；
B. according to the mass fraction, 5 parts of dried objects, 10 portions of dispersion activating agents, 3 parts of suspension thickeners, the molten adjuvant of 2 parts of oil, 40 are taken
Part water, 30min is stirred in 40 DEG C, adjusts pH to 7 to get dispersible type agricultural chemicals suspension agent.
Embodiment 2
Initiator are as follows: take potassium peroxydisulfate 5:3 in mass ratio be added ammonium persulfate mixing to get.
Viscosity reduction additive the preparation method comprises the following steps: take 2- acrylamide-2-methyl propane sulfonic 5:6:20 in mass ratio be added third
Olefin(e) acid, deionized water, are stirred 30min, obtain mixed liquor a, take initiator 3:0.8:15 in mass ratio be added sodium hydrogensulfite,
Deionized water is stirred 20min, obtains mixed liquor b, takes mixed liquor b 5:30 to be in mass ratio added dropwise in mixed liquor a, is passed through nitrogen
Gas shielded is stirred 90min in 85 DEG C, obtains stirring mixture, takes stirring mixture 6:15 in mass ratio that ethyl acetate is added,
50min is stood, takes precipitating dry to get viscosity reduction additive.
Solvent are as follows: take toluene 20:5 in mass ratio be added n,N-Dimethylformamide mixing to get.
Acid additive are as follows: take tartaric acid 10:7 in mass ratio be added lauric acid mixing to get.
Support dispersing matrixes object the preparation method comprises the following steps:
(1) take acid additive 3:5:15 in mass ratio that N is added, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, solvent are stirred in 60 DEG C
Mixing 30min is mixed, the boron trifluoride ether of acid additive quality 5% is added, is stirred 7h in 100 DEG C, is evaporated under reduced pressure, obtains
It is evaporated under reduced pressure object；
(2) take vacuum distillation object 5:3:15 in mass ratio that N is added, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, toluene must mix
Object is added the p-methyl benzenesulfonic acid of mixture quality 4%, is passed through nitrogen protection, is stirred 5h in 120 DEG C, vacuum distillation to get
Support dispersing matrixes object.
Disperse activating agent the preparation method comprises the following steps:
S1. it takes support dispersing matrixes object 9:10 in mass ratio that ethylene bromohyrin is added, adds support dispersing matrixes amount of substance 0.9%
P-methyl benzenesulfonic acid, be passed through nitrogen protection, be stirred 7h in 110 DEG C, be evaporated under reduced pressure, object a must be evaporated under reduced pressure, take vacuum distillation
Acrylic acid, distilled water is added in object a 8:3:15 in mass ratio, obtains mixture a, takes mixture a 30:5 in mass ratio that 2,2- connection is added
Pyridine adjusts pH to 9, adds the copper bromide of mixture a mass 5%, cooling in liquid nitrogen, thaws, for 24 hours then at 90 DEG C of heat preservations,
Obtain mixture b；
S2. it takes mixture b 10:5:20 in mass ratio that allyl polyglycol methyl ether, water is added, adds mixture b mass
10% 2,2- bipyridyl adjusts pH to 6, cooling through liquid nitrogen, thaws, obtains mixture c, and mixture c 20:3 in mass ratio is taken to be added
Copper bromide is stirred 15h in 25 DEG C, filters through alumina chromatographic column, filtrate is taken to disperse activating agent to obtain the final product.
Suspension thickener are as follows: take xanthan gum 5:3:20 in mass ratio be added pulullan polysaccharide, aluminum magnesium silicate mixing to get.
The molten adjuvant of oil are as follows: take Crodaret 5:5:10 in mass ratio that Emulsifier EL-60 is added, gathers
Ethylene glycol -400 mixing to get.
A kind of preparation method of dispersible type agricultural chemicals suspension agent, includes the following steps:
A. according to the mass fraction, 6 parts of viscosity reduction additives, 3 parts of n-octyl amines, 3 parts of dicyclohexylcarbodiimides, 50 parts of N- methyl pyrroles are taken
Pyrrolidone is stirred 3h in 500r/min, 60 DEG C, for 24 hours then at 65 DEG C of heat preservations, in 4 DEG C of standings 5h, suction filtration, take smoke filtrate by
The sodium hydroxide solution that mass fraction is 40% is added in mass ratio 3:15, is stirred 90min, filters, filter residue is taken to wash through methanol
It washs, it is dry, obtain dried object；
B. according to the mass fraction, 10 parts of dried objects, 20 portions of dispersion activating agents, 6 parts of suspension thickeners, the molten adjuvant of 5 parts of oil, 50 are taken
Part water, 60min is stirred in 50 DEG C, adjusts pH to 7.2 to get dispersible type agricultural chemicals suspension agent.
Embodiment 3
Initiator are as follows: take potassium peroxydisulfate 3:2 in mass ratio be added ammonium persulfate mixing to get.
Viscosity reduction additive the preparation method comprises the following steps: take 2- acrylamide-2-methyl propane sulfonic 3:5:13 in mass ratio be added third
Olefin(e) acid, deionized water, are stirred 25min, obtain mixed liquor a, take initiator 2:0.7:13 in mass ratio be added sodium hydrogensulfite,
Deionized water is stirred 13min, obtains mixed liquor b, takes mixed liquor b 2:13 to be in mass ratio added dropwise in mixed liquor a, is passed through nitrogen
Gas shielded is stirred 80min in 80 DEG C, obtains stirring mixture, takes stirring mixture 5:13 in mass ratio that ethyl acetate is added,
40min is stood, takes precipitating dry to get viscosity reduction additive.
Solvent are as follows: take toluene 15:4 in mass ratio be added n,N-Dimethylformamide mixing to get.
Acid additive are as follows: take tartaric acid 7:5 in mass ratio be added lauric acid mixing to get.
Support dispersing matrixes object the preparation method comprises the following steps:
(1) take acid additive 2:3:12 in mass ratio that N is added, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, solvent are stirred in 55 DEG C
Mixing 25min is mixed, the boron trifluoride ether of acid additive quality 3% is added, is stirred 6h in 95 DEG C, is evaporated under reduced pressure, must subtract
Press distillation；
(2) take vacuum distillation object 3:2:12 in mass ratio that N is added, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, toluene must mix
Object is added the p-methyl benzenesulfonic acid of mixture quality 2%, is passed through nitrogen protection, is stirred 3h in 115 DEG C, vacuum distillation to get
Support dispersing matrixes object.
Disperse activating agent the preparation method comprises the following steps:
S1. it takes support dispersing matrixes object 5:7 in mass ratio that ethylene bromohyrin is added, adds support dispersing matrixes amount of substance 0.6%
P-methyl benzenesulfonic acid is passed through nitrogen protection, is stirred 6h in 105 DEG C, and vacuum distillation must be evaporated under reduced pressure object a, take vacuum distillation object
Acrylic acid, distilled water is added in a 5:2:12 in mass ratio, obtains mixture a, takes mixture a 25:3 in mass ratio that 2,2- connection pyrrole is added
Pyridine adjusts pH to 8.5, adds the copper bromide of mixture a mass 3%, cooling in liquid nitrogen, thaws, then at 85 DEG C of heat preservation 20h,
Obtain mixture b；
S2. it takes mixture b 7:3:13 in mass ratio that allyl polyglycol methyl ether, water is added, adds mixture b mass 7%
2,2- bipyridyl, adjust pH to 5.5, it is cooling through liquid nitrogen, thaw, obtain mixture c, mixture c 15:2 in mass ratio is taken to be added
Copper bromide is stirred 13h in 23 DEG C, filters through alumina chromatographic column, filtrate is taken to disperse activating agent to obtain the final product.
Suspension thickener are as follows: take xanthan gum 4:2:13 in mass ratio be added pulullan polysaccharide, aluminum magnesium silicate mixing to get.
The molten adjuvant of oil are as follows: take Crodaret 3:3:7 in mass ratio that Emulsifier EL-60, poly- second is added
Glycol -400 mixing to get.
A kind of preparation method of dispersible type agricultural chemicals suspension agent, includes the following steps:
A. according to the mass fraction, 4 parts of viscosity reduction additives, 2 parts of n-octyl amines, 2 parts of dicyclohexylcarbodiimides, 45 parts of N- methyl pyrroles are taken
Pyrrolidone is stirred 2h in 500r/min, 55 DEG C, then at 60 DEG C of heat preservation 22h, in 3 DEG C of standing 4h, filters, take smoke filtrate by
The sodium hydroxide solution that mass fraction is 40% is added in mass ratio 2:13, is stirred 70min, filters, filter residue is taken to wash through methanol
It washs, it is dry, obtain dried object；
B. according to the mass fraction, 7 parts of dried objects, 15 portions of dispersion activating agents, 5 parts of suspension thickeners, the molten adjuvant of 3 parts of oil, 45 are taken
Part water, 50min is stirred in 45 DEG C, adjusts pH to 7.1 to get dispersible type agricultural chemicals suspension agent.
Comparative example 1: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking viscosity reduction additive.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking dispersion activating agent.
Comparative example 3: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking suspension thickener.
Comparative example 4: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking the molten adjuvant of oil.
Comparative example 5: the dispersible type agricultural chemicals suspension agent of company, Dafeng City production.
Above-described embodiment and dispersible type agricultural chemicals suspension agent prepared by comparative example are detected, according to GB/T1603-
2001 carry out suspensions stability tests, measure that the results are shown in Table 1.
Table 1:
In summary, dispersible type agricultural chemicals suspension agent effect of the invention is more preferable as can be seen from Table 1, is worth of widely use, with
The upper preferred mode only of the invention, is not intended to limit the invention, all within the spirits and principles of the present invention, is made
Any modification, equivalent substitution, improvement and etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of dispersible type agricultural chemicals suspension agent, which is characterized in that including viscosity reduction additive, dispersion activating agent, suspension thickener,
The molten adjuvant of oil；
The viscosity reduction additive the preparation method comprises the following steps: taking 2- acrylamide-2-methyl propane sulfonic 2 ~ 5:2 in mass ratio ~ 6:10 ~ 20
Addition acrylic acid, deionized water are stirred, and obtain mixed liquor a, take initiator 1 ~ 3:0.5 in mass ratio ~ 0.8:10 ~ 15 to be added sub-
Sodium bisulfate, deionized water are stirred, and obtain mixed liquor b, and 1 ~ 5:10 ~ 30 in mass ratio mixed liquor b is taken to be added dropwise to mixed liquor a
In, it is passed through nitrogen protection, is stirred, stirring mixture is obtained, takes stirring mixture 2 ~ 6:10 in mass ratio ~ 15 that acetic acid second is added
Ester is stood, and takes precipitating dry to get viscosity reduction additive.
2. dispersible type agricultural chemicals suspension agent according to claim 1, which is characterized in that the initiator are as follows: take persulfuric acid
Potassium 2 ~ 5:1 in mass ratio ~ 3 be added ammonium persulfate mixing to get.
3. dispersible type agricultural chemicals suspension agent according to claim 1, which is characterized in that the preparation side of the dispersion activating agent
Method are as follows:
S1. it takes support dispersing matrixes object 4 ~ 9:5 in mass ratio ~ 10 that ethylene bromohyrin is added, adds support dispersing matrixes amount of substance
0.4 ~ 0.9% p-methyl benzenesulfonic acid, is passed through nitrogen protection, is stirred, and vacuum distillation must be evaporated under reduced pressure object a, take vacuum distillation
Acrylic acid, distilled water is added in object a 3 ~ 8:1 in mass ratio ~ 3:10 ~ 15, obtains mixture a, take mixture a 20 ~ 30:1 in mass ratio ~
5 are added 2,2- bipyridyl, adjust pH to 8 ~ 9, add the copper bromide of mixture a mass 1 ~ 5%, cooling in liquid nitrogen, thaw,
It is kept the temperature then at 80 ~ 90 DEG C, obtains mixture b；
S2. it takes mixture b 5 ~ 10:2 in mass ratio ~ 5:10 ~ 20 that allyl polyglycol methyl ether, water is added, adds mixing
2, the 2- bipyridyl of object b mass 5 ~ 10% adjusts pH to 5 ~ 6, cooling through liquid nitrogen, thaws, obtains mixture c, take mixture c by matter
Amount is added copper bromide than 10 ~ 20:1 ~ 3 and is stirred, and filters, filtrate is taken to disperse activating agent to obtain the final product.
4. dispersible type agricultural chemicals suspension agent according to claim 3, which is characterized in that the support dispersion in the step S1
Matrix object the preparation method comprises the following steps:
(1) take acid additive 1 ~ 3:2 in mass ratio ~ 5:10 ~ 15 that N is added, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, solvent stir
Mixing is mixed, the boron trifluoride ether for adding acid additive quality 2 ~ 5% is stirred, and vacuum distillation obtains vacuum distillation object；
(2) it takes and is evaporated under reduced pressure object 2 ~ 5:1 in mass ratio ~ addition N of 3:10 ~ 15, N- dihydroxy ethyl -3- amidos propionic acid methyl esters, toluene,
Mixture is obtained, the p-methyl benzenesulfonic acid of mixture quality 1 ~ 4% is added, is passed through nitrogen protection, is stirred, is evaporated under reduced pressure to get branch
Support dispersing matrixes object.
5. dispersible type agricultural chemicals suspension agent according to claim 4, which is characterized in that the acid addition in the step (1)
Agent are as follows: take tartaric acid 5 ~ 10:2 in mass ratio ~ 7 be added lauric acid mixing to get.
6. dispersible type agricultural chemicals suspension agent according to claim 4, which is characterized in that the solvent in the step (1) are as follows:
Take toluene 10 ~ 20:3 in mass ratio ~ 5 be added n,N-Dimethylformamide mixing to get.
7. dispersible type agricultural chemicals suspension agent according to claim 1, which is characterized in that the suspension thickener are as follows: take Huang
Virgin rubber 3 ~ 5:1 in mass ratio ~ 3:10 ~ 20 be added pulullan polysaccharide, aluminum magnesium silicate mixing to get.
8. dispersible type agricultural chemicals suspension agent according to claim 1, which is characterized in that the molten adjuvant of oil are as follows: take poly-
Ethylene oxide rilanit special 2 ~ 5:2 in mass ratio ~ 5:5 ~ 10 be added Emulsifier EL-60, polyethylene glycol-400 mixing to get.
9. a kind of preparation method of the dispersible type agricultural chemicals suspension agent as described in claim 1 ~ 8 any one, which is characterized in that
The preparation method includes the following steps:
A. according to the mass fraction, 3 ~ 6 parts of viscosity reduction additives, 1 ~ 3 part of n-octyl amine, 1 ~ 3 part of dicyclohexylcarbodiimide, 40 ~ 50 are taken
Part N-Methyl pyrrolidone is stirred, and is kept the temperature then at 55 ~ 65 DEG C, is stood in 1 ~ 4 DEG C, is filtered, take smoke filtrate in mass ratio 1 ~
3:5 ~ 15 is added sodium hydroxide solution and is stirred, and filters, filter residue is taken to wash through methanol, dry, obtains dried object；
B. according to the mass fraction, take 5 ~ 10 parts of dried objects, 10 ~ 20 parts of dispersion activating agents, 3 ~ 6 parts of suspension thickeners, 2 ~ 5 parts of oil molten
Adjuvant, 40 ~ 50 parts of water are stirred, and adjust pH to 7 ~ 7.2 to get dispersible type agricultural chemicals suspension agent.
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|---|---|---|---|---|
| US5538723A (en) * | 1994-03-02 | 1996-07-23 | Petrolite Corporation | Method for suppressing the viscosity of bioinsecticide slurries and related slurries |
| CN102002134A (en) * | 2010-11-05 | 2011-04-06 | 济南大学 | Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof |
| CN106359431A (en) * | 2016-08-26 | 2017-02-01 | 安徽久易农业股份有限公司 | Corn-field weed killer |
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2019
- 2019-02-25 CN CN201910135434.5A patent/CN109997845A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5538723A (en) * | 1994-03-02 | 1996-07-23 | Petrolite Corporation | Method for suppressing the viscosity of bioinsecticide slurries and related slurries |
| CN102002134A (en) * | 2010-11-05 | 2011-04-06 | 济南大学 | Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof |
| CN106359431A (en) * | 2016-08-26 | 2017-02-01 | 安徽久易农业股份有限公司 | Corn-field weed killer |
Non-Patent Citations (1)
| Title |
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| 张龙军 等: "不同链转移剂制备丙烯酸/2-丙烯酰胺基-2-甲基丙磺酸共聚物及其降黏性能研究", 《精细石油化工》 * |
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Application publication date: 20190712 |