CN109997847A - Alkyd resin/pesticide nano lotion and preparation method thereof - Google Patents
Alkyd resin/pesticide nano lotion and preparation method thereof Download PDFInfo
- Publication number
- CN109997847A CN109997847A CN201910363551.7A CN201910363551A CN109997847A CN 109997847 A CN109997847 A CN 109997847A CN 201910363551 A CN201910363551 A CN 201910363551A CN 109997847 A CN109997847 A CN 109997847A
- Authority
- CN
- China
- Prior art keywords
- alkyd resin
- pesticide
- water
- optional
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
This application discloses a kind of alkyd resin/pesticide nano lotion and preparation method thereof, the alkyd resin/pesticide nano lotion includes water-insoluble pesticide, alkyd resin and water.The average hydration partial size of drug-carried fine particle is 30~250nm in the alkyd resin/pesticide nano lotion, solid content is 10-50%, alkyd resin drugloading rate is 0.01~50%, encapsulation rate is not less than 90%, possesses good dispersibility and stability, and blade face adhesion is good, active length, bioavailability are high, there are slow controlled release properties simultaneously, it can be used with Direct spraying, and carrier is biodegradable, it is environmentally protective, safe and efficient.
Description
Technical field
The invention belongs to technical field of pesticide, specifically, the present invention relates to a kind of alkyd resin/pesticide nano lotion and
Preparation method.
Background technique
Pesticide is as a kind of important agricultural chemicals, in sides such as pest control, protection crops and raising crop yields
Face is most important and is widely applied.However, due to the shadow of the factors such as the insecticide-applying way of traditional agriculture and environmental condition
It rings, pesticide eventually arrives at the effective rate of utilization of crop target less than 30%, and harmful organism reality is by dose less than 0.1%.At present
The common formulations of pesticide are mainly missible oil and wettable powder in the market, these conventional dosage forms also band while large-scale use
Vast resources waste and environmental pollution are come.Therefore, the research and development of efficient, green pesticides new formulation are concerned.
Pesticide load technology is the effective way for overcoming traditional formulations of pesticide defect.By the way that pesticide and carrier material are carried out
The modes such as package and coupling can significantly improve pesticide in the adhesive force of blade surface, extend the pesticide residence time, hold pesticide
Continuous stable release is possibly realized, to improve pesticide efficacy, reduces the loss and pollution of pesticide.However, current market
On pesticide load preparation partial size be usually micron order, big partial size is easy to cause its water dispersible poor, and application process is easily drawn
Drop is played to slide, it is the problems such as dust is elegant, poor to the adhesion, permeability and bioavilability of crop target.Tradition simultaneously
Preparation flow complex process, the more difficult to control and poor repeatability of pesticide load preparation.
Therefore, existing pesticide is further improved.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of alkyd resin/pesticide nano lotion and preparation method thereof.The alkyd resin/pesticide nano lotion
The average hydration partial size of middle drug-carried fine particle be 30~250nm, solid content 10-50%, alkyd resin drugloading rate be 0.01~
50%, encapsulation rate is not less than 90%, possesses good dispersibility and stability, and blade face adhesion is good, active length, bioavailability
Height, while there are slow controlled release properties, it can be used with Direct spraying, and carrier is biodegradable, it is environmentally protective, safe and efficient.
In one aspect of the invention, according to the present invention the invention proposes a kind of alkyd resin/pesticide nano lotion
Embodiment, the alkyd resin/pesticide nano lotion include: water-insoluble pesticide, alkyd resin and water.According to embodiments of the present invention
Alkyd resin/pesticide nano lotion, the carrier by using alkyd resin as water-insoluble pesticide, alkyd resin be can be again
Production-goods source, it is low in cost；Alkyd resin is biodegradable, and the carrier as water-insoluble pesticide is environmentally protective；By in alkyd
Hydrophilic radical is introduced in resin backbone, without additional emulsifier can prepare can stable dispersion in water water alcohol acid tree
Rouge has preferable environmental benefit；Carrier material of the alkyd resin as water-insoluble pesticide, can be improved medicine-carried system to agriculture
The adhesion on crop blade face, the blade face for reducing medicament is missed the target loss, to improve the effective rate of utilization and bioavilability of pesticide.
The medium of medicine-carried system is water, is free of organic solvent, economy and environmental benefit are excellent.Alkyd resin/pesticide in the application is received
The medicine-carried system of rice milk liquid has Nano Particle, the minimum reachable 30nm of partial size, and particle size distribution range is narrow, and stability is good；Together
When nanoscale medicine-carried system, be conducive to improve pesticide and crop surface contact area, increase pesticide in crops leaf
The adhesion and permeability in face, substantially reduce the loss of pesticide, improve the effective rate of utilization and drug effect of pesticide；Further, it receives
The medicine-carried system of metrical scale increases the contact area of pesticide and pest target, and it is living to the desinsection of pest target can to increase pesticide
Property.Alkyd resin/pesticide nano emulsion dispersibility is good, and lotion can store 12 months or more.Alkyd resin/pesticide nano lotion
For the drugloading rate of carrier up to 50%, encapsulation rate is not less than 90%, and can adjust emulsion solid content and drugloading rate according to actual needs,
It has wide range of applications.Alkyd resin/pesticide nano lotion has medicine sustained and controlled release performance, can maintain longer administration time,
Administration number of times and dosage are reduced, to improve bioavailability, reduces pesticide cost.
In addition, alkyd resin according to the above embodiment of the present invention/pesticide nano lotion can also have it is following additional
Technical characteristic:
In some embodiments of the invention, the mass ratio of the water-insoluble pesticide, the alkyd resin and the water
For 0.01~25:9.99~49.99:50~90.It can further improve alkyd resin/pesticide nano lotion quality as a result,.
In some embodiments of the invention, the alkyd resin be vegetable oil with polyalcohol, binary acid or acid anhydrides, contain
Three and above functional group's polyacid or aggregated react of acid anhydrides obtain.The cost of alkyd resin can be further decreased as a result,
Improve the biodegradability of alkyd resin.
In some embodiments of the invention, the vegetable oil and the polyalcohol, the binary acid or acid anhydrides, described contain
There are three and the mass ratio of above functional group's polyacid or acid anhydrides be 10:2~9:0.5~9.5:1.5~3.It as a result, can be further
Promote the quality of alkyd resin.
In some embodiments of the invention, the vegetable oil, the polyalcohol, the binary acid or acid anhydrides and described contain
There are three and above functional group's polyacid or acid anhydrides in the ratio between-OH integral molar quantity and-COOH integral molar quantity be 1.1~1.4.By
This, can further promote the quality of alkyd resin.
In some embodiments of the invention, the acid value of the alkyd resin is 35~70mgKOH/g.It as a result, can be into one
Step promotes the quality of alkyd resin.
In some embodiments of the invention, the vegetable oil is selected from linseed oil, soya-bean oil, tung oil, castor oil, coconut oil
At least one of with cottonseed oil.The cost that alkyd resin can be further decreased as a result, improves the biodegradable of alkyd resin
Property.
In some embodiments of the invention, the polyalcohol is selected from glycerol, pentaerythrite, trimethylolpropane, three
At least one of hydroxymethyl ethane, ethylene glycol, propylene glycol, butanediol and neopentyl glycol.It can further improve alkyd tree as a result,
The quality of rouge.
In some embodiments of the invention, the binary acid or acid anhydrides be selected from M-phthalic acid, phthalic anhydride,
At least one of terephthalic acid (TPA), maleic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride.It as a result, can be into one
Step improves the quality of alkyd resin.
In some embodiments of the invention, it is described containing there are three and above functional group's polyacid or acid anhydrides for selected from inclined benzene
At least one of three acid anhydrides, pyromellitic dianhydride.Containing there are three and above functional group's polyacid or acid anhydrides be alkyd resin master
Chain introduces hydrophilic radical, thus, it is possible to the combination by selecting different polyacids or acid anhydrides, realize medicine-carried system nanosizing and
High stability.
In some embodiments of the invention, the water-insoluble pesticide is selected from gamma cyhalothrin, cyfluthrin chrysanthemum
Ester, Biphenthrin, decis, fenvalerate, thiacloprid, clothianidin, Hostathion, carbosulfan, avermectin, acetyl ammonia
At least one of base avermectin, ivermectin, chlorine pyrazothion, phoxim, Rynaxypyr.
In some embodiments of the invention, the water-insoluble pesticide is selected from gamma cyhalothrin, cyfluthrin chrysanthemum
At least one of ester, avermectin, ivermectin, chlorine pyrazothion and phoxim.
In another aspect of the invention, above-mentioned alkyd resin/pesticide nano lotion is prepared the invention proposes a kind of
Method, according to an embodiment of the invention, this method comprises:
(1) alkyd resin is mixed into neutralization with lye, to obtain waterborne alkyd resin；
(2) water-insoluble pesticide is mixed with cosolvent, to obtain the pesticide solution；
(3) waterborne alkyd resin, the pesticide solution, emulsifier solution/water are mixed, and through phase reversal and decompression
Distillation processing, to obtain alkyd resin/pesticide nano lotion.
It is according to an embodiment of the present invention to prepare alkyd resin/pesticide nano lotion method, by using high speed in situ phase
Reversal process prepares alkyd resin/pesticide nano lotion, relative to the preparation method of traditional pesticide medicine-carried system, system of the invention
Preparation Method is simple and efficient and reproducible, easy to industrialized production.Load by using alkyd resin as water-insoluble pesticide
Body, alkyd resin is renewable resource, low in cost；Alkyd resin is biodegradable, and the carrier as water-insoluble pesticide is green
Colour circle is protected；By introducing hydrophilic radical on alkyd backbone, can prepare without additional emulsifier can be stable in water
The aqueous alkide resin of dispersion has preferable environmental benefit；Carrier material of the alkyd resin as water-insoluble pesticide, can be with
Medicine-carried system is improved to the adhesion of corps leaf surface, the blade face for reducing medicament is missed the target loss, to improve effective benefit of pesticide
With rate and bioavilability.Alkyd resin/pesticide nano lotion medicine-carried system in the application has Nano Particle, partial size
Minimum reachable 30nm, and particle size distribution range is narrow, stability is good；The medicine-carried system of nanoscale simultaneously is conducive to improve pesticide
With the contact area of crop surface, increases pesticide in the adhesion and permeability of corps leaf surface, substantially reduce the stream of pesticide
It loses, improves the effective rate of utilization and drug effect of pesticide；Further, the medicine-carried system of nanoscale makes pesticide and pest target
Contact area increases, and can increase pesticide to the insecticidal activity of pest target.Alkyd resin/pesticide nano emulsion dispersibility is good,
Lotion can store 12 months or more.Up to 50%, encapsulation rate is not less than alkyd resin/pesticide nano emulsion carriers drugloading rate
90%, and emulsion solid content and drugloading rate can be adjusted according to actual needs, it has wide range of applications.Alkyd resin/pesticide nano cream
Liquid has medicine sustained and controlled release performance, can maintain longer administration time, reduces administration number of times and dosage, to improve biological benefit
With rate, pesticide cost is reduced.
In addition, alkyd resin/pesticide nano lotion method according to the above embodiment of the present invention for preparing can also have
Following additional technical characteristic:
In some embodiments of the invention, in step (1), the lye be in organic base or inorganic base extremely
It is one of few.Be conducive to improve the quality of waterborne alkyd resin as a result,.
In some embodiments of the invention, in step (1), the organic base is in triethylamine, trimethylamine
At least one.It can further improve the quality of waterborne alkyd resin as a result,.
In some embodiments of the invention, in step (1), the inorganic base is in ammonium hydroxide and sodium hydroxide
At least one.It can further improve the quality of waterborne alkyd resin as a result,.
In some embodiments of the invention, in step (1), the mass ratio of the alkyd resin and the lye is
10:0.5~1.5.It can further improve the quality of waterborne alkyd resin as a result,.
In some embodiments of the invention, in step (2), the cosolvent is selected from ethyl acetate, ethyl alcohol, first
At least one of alcohol, isopropanol, acetone, butanone, hexamethylene and n-hexane.Be conducive to improve the quality of the pesticide solution as a result,.
In some embodiments of the invention, in step (2), the boiling point of the cosolvent is 50~100 DEG C.As a result,
It can further improve the quality of the pesticide solution.
In some embodiments of the invention, in step (2), the quality of the water-insoluble pesticide and the cosolvent
Than for 1:0.5~2.It can further improve the quality of the pesticide solution as a result,.
In some embodiments of the invention, in step (3), the emulsifier solution includes anion emulsifier and non-
Ionic emulsifying agent.Be conducive to improve the quality of emulsifier as a result,.
In some embodiments of the invention, in step (3), the anion emulsifier be selected from alkyl sulfate and
At least one of alkylbenzene sulfonate.It can further improve the quality of emulsifier as a result,.
In some embodiments of the invention, in step (3), the nonionic emulsifier is selected from alkyl phenol polyoxy second
At least one of alkene ethers, Tweens and this disk class.It can further improve the quality of emulsifier as a result,.
In some embodiments of the invention, the quality of emulsifier is the alkyd resin quality in the emulsifier solution
0~3%.It can further improve the quality of emulsifier as a result,.
In some embodiments of the invention, in step (3), the waterborne alkyd resin and the pesticide solution, institute
Stating emulsifier solution/water mass ratio is 9.99~49.99:0.02~60:50~91.5.It can further improve as a result,
Alkyd resin/pesticide nano lotion quality.
In some embodiments of the invention, in step (3), the mixing speed of the phase reversal is 1000~2000r/
min.It can further improve alkyd resin/pesticide nano lotion quality as a result,.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is according to an embodiment of the invention to prepare alkyd resin/pesticide nano lotion method flow schematic diagram；
Fig. 2 is that embodiment 1 prepares resulting alkyd resin/lambda-cyhalothrin nanoemulsion liquid transmission electron microscope
Figure.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In one aspect of the invention, according to the present invention the invention proposes a kind of alkyd resin/pesticide nano lotion
Embodiment, the alkyd resin/pesticide nano lotion include: water-insoluble pesticide, alkyd resin and water.Further, above-mentioned alcohol
In acid resin/pesticide nano lotion, the mass ratio of water-insoluble pesticide, alkyd resin and water can for 0.01~25:9.99~
49.99:50~90.Inventors have found that water-insoluble pesticide dosage is excessively high or water consumption is very few will lead to system viscosity mistake
Greatly, clad ratio reduces, and then causes alkyd resin/pesticide nano emulsion system unstable.
According to one embodiment of present invention, alkyd resin be vegetable oil and polyalcohol, binary acid or acid anhydrides, contain there are three
And above functional group's polyacid or aggregated react of acid anhydrides obtain.Specifically, vegetable oil and polyalcohol are mixed, in stirring bar
150~200 DEG C are gradually heated under part, backward reaction system in binary acid or acid anhydrides is added, be continuously heating to 200~240
DEG C, it carries out under nitrogen protection esterification 1-3 hours, constantly separation water outlet during the reaction, until the acid value of reactant
Less than 10mgKOH/g.Reaction system is cooled to 140~160 DEG C later, will then contain there are three and above functional group's polyacid
Or acid anhydrides is added in reaction system, is warming up to 160~190 DEG C, the reaction was continued 0.5-3 hours, constantly measures in reaction process
Reactant acid value stops reaction when acid value reaches 35~70mgKOH/g, obtains alkyd resin.Inventors have found that by using
Carrier of the alkyd resin as water-insoluble pesticide, alkyd resin is renewable resource, low in cost；Alkyd resin biological can drop
Solution, the carrier as water-insoluble pesticide are environmentally protective；By introducing hydrophilic radical on alkyd backbone, it is not necessarily to additional cream
Agent can prepare can stable dispersion in water aqueous alkide resin, there is preferable environmental benefit；Alkyd resin conduct
Medicine-carried system can be improved to the adhesion of corps leaf surface in the carrier material of water-insoluble pesticide, and the blade face for reducing medicament is de-
Target is lost, to improve the effective rate of utilization and bioavilability of pesticide.
A specific embodiment according to the present invention, vegetable oil and polyalcohol, binary acid or acid anhydrides, containing there are three or more
The mass ratio of functional group's polyacid or acid anhydrides can be 10:2~9:0.5~9.5:1.5~3, such as can be 10:2/3/4/5/
6/7/8/9:0.5/1.5/2.5/3.5/4.5/5.5/6.5/7.5/8.5/9.5:1.5/2/2. 5/3.Inventors have found that vegetable oil
The excessively high alkyd resin hydrophily that will lead to of dosage is insufficient, alkyd resin/pesticide nano lotion can not be made, vegetable oil consumption is too low
It is too strong to will lead to alkyd resin hydrophily, drug delivery amount is low.Further, vegetable oil, polyalcohol, binary acid or acid anhydrides and contain
There are three and above functional group's polyacid or acid anhydrides in the ratio between-OH integral molar quantity and-COOH integral molar quantity can be 1.1~1.4,
It such as can be 1.1,1.2,1.3,1.4, preferably 1.2.Inventors have found that-OH ratio is too low to will lead to alkyd resin hydrophily
Alkyd resin/pesticide nano lotion can not be made in deficiency, and the excessively high alkyd resin hydrophily that will lead to of-OH ratio is too strong, and drug carries
Dose is low.Further, vegetable oil can in linseed oil, soya-bean oil, tung oil, castor oil, coconut oil and cottonseed oil extremely
It is one of few.Inventors have found that vegetable oil is renewable resource, the raw material using vegetable oil as alkyd resin can not only save stone
Oily resource, moreover it is possible to assign alkyd resin biodegradable characteristics.Further, polyalcohol can for selected from glycerol, pentaerythrite,
At least one of trimethylolpropane, trimethylolethane, ethylene glycol, propylene glycol, butanediol and neopentyl glycol, preferably three hydroxyls
Methylpropane and glycerol.Further, binary acid or acid anhydrides can be selected from M-phthalic acid, phthalic anhydride, to benzene two
At least one of formic acid, maleic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride.Further, there are three containing
And above functional group's polyacid or acid anhydrides can be for selected from least one of trimellitic anhydrides, pyromellitic dianhydride.Inventor
It was found that containing there are three and above functional group's polyacid or acid anhydrides can introduce hydrophilic radical for alkyd backbone, thus, it is possible to lead to
The combination for selecting different polyacids or acid anhydrides is crossed, realizes the nanosizing and high stability of medicine-carried system.The load medicine body of nanoscale
System, be conducive to improve pesticide and crop surface contact area, increase pesticide corps leaf surface adhesion and permeability,
The loss for substantially reducing pesticide improves the effective rate of utilization and drug effect of pesticide；The medicine-carried system of nanoscale makes pesticide and evil
The contact area of worm target increases, and can increase pesticide to the insecticidal activity of pest target.
The acid value of still another embodiment in accordance with the present invention, alkyd resin can be 35~70mgKOH/g, such as can be
35mgKOH/g、40mgKOH/g、45mgKOH/g、50mgKOH/g、55mgKOH/g、60mgKOH/g、65mgKOH/g、
70mgKOH/g.Inventors have found that the too low resin hydrophily that will lead to of alkyd resin acid value is insufficient, alkyd resin/agriculture can not be made
Medicine nanoemulsions, the excessively high hydrophily that will lead to gained alkyd resin of acid value is excessively high or even completely water-soluble, equally can not be by pesticide
It is coated in emulsion particle and alkyd resin/pesticide nano lotion is made.
According to still another embodiment of the invention, water-insoluble pesticide can be for selected from gamma cyhalothrin, cyfluthrin
Pyrethroids, Biphenthrin, decis, fenvalerate, thiacloprid, clothianidin, Hostathion, carbosulfan, avermectin, acetyl
Amino avermectin, ivermectin, chlorine pyrazothion, phoxim, Rynaxypyr, preferably gamma cyhalothrin, fluorine chlorine
At least one of Cyano chrysanthemate, avermectin, ivermectin, chlorine pyrazothion and phoxim.
According to an embodiment of the invention, above-mentioned alkyd resin/pesticide nano lotion at least has the advantages that one of what follows:
In terms of carrier material, one of primary raw material of carrier alkyd resin of medicine-carried system of the present invention is vegetable oil, is planted
Object glossy dark green mulberry is safe, at low cost and biodegradable；The medium of medicine-carried system is water simultaneously, is free of organic solvent, economy and ring
Border benefit is excellent；
In terms of partial size, alkyd resin of the invention/pesticide medicine-carried system has Nano Particle, and partial size is minimum reachable
30nm, particle diameter distribution is narrow, and stability is good.Meanwhile the medicine-carried system of nanoscale improves contact of the pesticide with crop surface
Area increases pesticide in the adhesion and permeability of corps leaf surface, substantially reduces the loss of pesticide, to improve pesticide
Effective rate of utilization and drug effect.Further, the medicine-carried system of nanoscale may make the contact area of pesticide and pest target to increase
Add, and then increases the insecticidal activity to pest target；
Emulsion particle is small in terms of stability of emulsion, in alkyd resin/pesticidal emulsion of the invention and favorable dispersibility, lotion
It can store 12 months or more；
Prescription face is being carried, up to 50%, encapsulation rate is not less than alkyd resin of the invention/pesticide nano lotion drugloading rate
90%.Alkyd resin can be with the water-insoluble pesticide of payload, and can adjust emulsion solid content and drugloading rate according to actual needs,
It has wide range of applications；
In terms of farm chemical release, alkyd resin of the invention/pesticide medicine-carried system has medicine sustained and controlled release performance.Pass through agriculture
The slow release of medicine can maintain longer administration time, reduce administration number of times and dosage, to improve bioavailability, reduce
Pesticide cost；
In terms of adhesiveness, the present invention uses alkyd resin that load can be improved as the carrier material of water-insoluble pesticide
Medicine body system reduces medicament and misses the target losss from blade face to the adhesion of corps leaf surface, thus improve the effective rate of utilization of pesticide with
Bioavilability.
Alkyd resin according to an embodiment of the present invention/pesticide nano lotion, by using alkyd resin as water-insoluble
The carrier of pesticide, alkyd resin is renewable resource, low in cost；Alkyd resin is biodegradable, is used as water-insoluble pesticide
Carrier it is environmentally protective；By introducing hydrophilic radical on alkyd backbone, can prepare without additional emulsifier can be
The aqueous alkide resin of stable dispersion in water has preferable environmental benefit；Carrier of the alkyd resin as water-insoluble pesticide
Medicine-carried system can be improved to the adhesion of corps leaf surface in material, and the blade face for reducing medicament is missed the target loss, to improve pesticide
Effective rate of utilization and bioavilability.The medium of medicine-carried system is water, is free of organic solvent, economy and environmental benefit are excellent.
Alkyd resin/pesticide nano lotion medicine-carried system in the application has Nano Particle, the minimum reachable 30nm of partial size, and grain
Diameter narrow distribution range, stability are good；The medicine-carried system of nanoscale simultaneously is conducive to improve contact of the pesticide with crop surface
Area increases pesticide in the adhesion and permeability of corps leaf surface, substantially reduces the loss of pesticide, improve effective benefit of pesticide
With rate and drug effect；Further, the medicine-carried system of nanoscale increases the contact area of pesticide and pest target, can increase
Insecticidal activity of the pesticide to pest target.Alkyd resin/pesticide nano emulsion dispersibility is good, lotion can store 12 months with
On.For alkyd resin/pesticide nano emulsion carriers drugloading rate up to 50%, encapsulation rate is not less than 90%, and can be according to practical need
It asks and adjusts emulsion solid content and drugloading rate, have wide range of applications.Alkyd resin/pesticide nano lotion has medicine sustained and controlled release
Can, longer administration time can be maintained, administration number of times and dosage are reduced, to improve bioavailability, reduces pesticide cost.
In another aspect of the invention, above-mentioned alkyd resin/pesticide nano lotion is prepared the invention proposes a kind of
Method, according to an embodiment of the invention, with reference to Fig. 1, this method comprises:
S100: alkyd resin is mixed into neutralization with lye
In the step, alkyd resin is mixed into neutralization with lye, to obtain waterborne alkyd resin.Inventors have found that alkali
Neutralization reaction can occur with-the COOH on alkyd resin strand, form hydrophilic radical, assign alkyd resin hydrophily.It is logical
The carrier using alkyd resin as water-insoluble pesticide is crossed, alkyd resin is renewable resource, low in cost；Alkyd resin can
Biodegrade, the carrier as water-insoluble pesticide are environmentally protective；By introducing hydrophilic radical on alkyd backbone, it is not necessarily to
Additional emulsifier can prepare can stable dispersion in water aqueous alkide resin, there is preferable environmental benefit；Alkyd tree
Carrier material of the rouge as water-insoluble pesticide can be improved medicine-carried system to the adhesion of corps leaf surface, reduce medicament
Blade face is missed the target loss, to improve the effective rate of utilization and bioavilability of pesticide.
According to one embodiment of present invention, lye can be selected from least one of organic base and inorganic base, specifically
, organic base can be for selected from least one of triethylamine, trimethylamine, inorganic base can be in ammonium hydroxide and sodium hydroxide
At least one of.Further, the mass ratio of alkyd resin and lye can be 10:0.5~1.5.Inventors have found that lye is used
It is insufficient that amount will lead to alkyd resin degree of neutralization very little, can not phase reversal lotion is made, lye dosage can excessively make system ionic
Intensity increases, and will lead to system demulsification.
S200: water-insoluble pesticide is mixed with cosolvent
In the step, water-insoluble pesticide is mixed with cosolvent, to obtain the pesticide solution.By using cosolvent,
Be advantageously implemented the dissolution of water-insoluble pesticide, obtain the pesticide solution so that the pesticide solution it is subsequent with waterborne alkyd resin, emulsification
Agent is mixed with alkyd resin/pesticide nano lotion and is possibly realized.
According to one embodiment of present invention, cosolvent can be for selected from ethyl acetate, ethyl alcohol, methanol, isopropanol, third
At least one of ketone, butanone, hexamethylene and n-hexane, ethyl acetate and ethyl alcohol.Further, the boiling point of cosolvent can
Think 50~100 DEG C, such as can be 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C.Inventors have found that the boiling of cosolvent
Point is too low, causes it to volatilize in N-process acutely, neutralizes not exclusively, and cosolvent boiling point is excessively high, and it is logical to be unfavorable for the later period
Vacuum distillation is crossed to remove it from system.Further, the mass ratio of water-insoluble pesticide and cosolvent can for 1:0.5~
2.Inventors have found that cosolvent dosage is too low can not to be effectively reduced alkyd resin viscosity, emulsion particle diameter obtained is distributed poor, dosage
It is excessively high, Component Vectors can be dissolved, alkyd resin/pesticidal emulsion can not be made up of phase reversal.
S300: waterborne alkyd resin, the pesticide solution, emulsifier solution/water are mixed, and through phase reversal and vacuum distillation at
Reason
In the step, waterborne alkyd resin, the pesticide solution, emulsifier solution/water are mixed, and is steamed through phase reversal and decompression
Processing is evaporated, to obtain alkyd resin/pesticide nano lotion.Specifically, can be by waterborne alkyd resin, the pesticide solution, emulsification
Agent solution mixing, and handled through phase reversal and vacuum distillation, it, can also be by water to obtain alkyd resin/pesticide nano lotion
Based alkyd, the pesticide solution, water mixing, and handled through phase reversal and vacuum distillation, to obtain alkyd resin/pesticide nano
Lotion.Inventors have found that in high-speed stirred inversion process, alkyd resin, can will be non-aqueous as amphiphilic macromolecular
Property the pesticide solution drop be packed in its hydrophobic chain intersegmental part, hydrophilic radical close to water side, thus as carrier help drug
Disperse in water.Carrier can substantially reduce alkyd resin/pesticide nano lotion surface can, enhancing pesticide on plant surface or
Wetting, spread and the adhesive ability on pest surface, to improve drug effect.Alkyd is prepared by using high speed in situ phase inversion
Resin/pesticide nano lotion, relative to the preparation method of traditional pesticide medicine-carried system, preparation method of the invention is simple and efficient
And it is reproducible, it is easy to industrialized production.Alkyd resin/pesticide nano lotion medicine-carried system in the application has nanoscale
Partial size, the minimum reachable 30nm of partial size, and particle size distribution range is narrow, stability is good；The medicine-carried system of nanoscale simultaneously, is conducive to
The contact area of pesticide and crop surface is improved, increases pesticide in the adhesion and permeability of corps leaf surface, substantially reduces
The loss of pesticide improves the effective rate of utilization and drug effect of pesticide；Further, the medicine-carried system of nanoscale makes pesticide and evil
The contact area of worm target increases, and can increase pesticide to the insecticidal activity of pest target.Alkyd resin/pesticide nano emulsion dispersion
Property is good, and lotion can store 12 months or more.Alkyd resin/pesticide nano emulsion carriers drugloading rate is up to 50%, encapsulation rate
Not less than 90%, and emulsion solid content and drugloading rate can be adjusted according to actual needs, have wide range of applications.Alkyd resin/pesticide
Nanoemulsions have medicine sustained and controlled release performance, can maintain longer administration time, administration number of times and dosage are reduced, to improve
Bioavailability reduces pesticide cost.
According to one embodiment of present invention, emulsifier solution includes anion emulsifier and nonionic emulsifier, yin from
Sub- emulsifier and nonionic emulsifier can realize compounding.Specifically, anion emulsifier can be for selected from alkyl sulfate and alkane
At least one of base benzene sulfonate.Nonionic emulsifier can be for selected from alkyl phenol polyoxyethylene ether class, Tweens and this disk
At least one of class.Inventors have found that emulsion particle diameter made from the compounding of anion emulsifier and nonionic emulsifier is than independent
It is smaller, more uniform using lotion prepared by the two one.
Still another embodiment in accordance with the present invention, the quality of emulsifier can be alkyd resin quality in emulsifier solution
0~3%, such as can be 0%, 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3.0%.Inventors have found that emulsifier adds
Enter to further decrease alkyd resin/pesticide nano lotion surface energy, enhances it in the profit on plant surface or pest surface
Wet and spread ability.
The mass ratio of still another embodiment in accordance with the present invention, waterborne alkyd resin and the pesticide solution, emulsifier solution can
Think 9.99~49.99:0.02~60:50~91.5, such as can be 9.99/15/19.99/25/29.99/35/39.99/
45/49.99:0.02/10/20/30/40/50/60:50/60/70/80/90/91.5.Inventors have found that the pesticide solution dosage mistake
High or emulsifier solution is too low to will lead to alkyd resin/pesticide nano emulsion intercalation method decline.
According to still another embodiment of the invention, the mixing speed of phase reversal can be 1000~2000r/min.Inventor
All phase reversal effect can be caused undesirable it was found that phase reversal stirring rate is too high or too low, so that obtained alkyd resin/pesticide
Nanoemulsions stability is poor.
It is according to an embodiment of the present invention to prepare alkyd resin/pesticide nano lotion method, by using high speed in situ phase
Reversal process prepares alkyd resin/pesticide nano lotion, relative to the preparation method of traditional pesticide medicine-carried system, system of the invention
Preparation Method is simple and efficient and reproducible, easy to industrialized production.Load by using alkyd resin as water-insoluble pesticide
Body, alkyd resin is renewable resource, low in cost；Alkyd resin is biodegradable, and the carrier as water-insoluble pesticide is green
Colour circle is protected；By introducing hydrophilic radical on alkyd backbone, can prepare without additional emulsifier can be stable in water
The aqueous alkide resin of dispersion has preferable environmental benefit；Carrier material of the alkyd resin as water-insoluble pesticide, can be with
Medicine-carried system is improved to the adhesion of corps leaf surface, the blade face for reducing medicament is missed the target loss, to improve effective benefit of pesticide
With rate and bioavilability.Alkyd resin/pesticide nano lotion medicine-carried system in the application has Nano Particle, partial size
Minimum reachable 30nm, and particle size distribution range is narrow, stability is good；The medicine-carried system of nanoscale simultaneously is conducive to improve pesticide
With the contact area of crop surface, increases pesticide in the adhesion and permeability of corps leaf surface, substantially reduce the stream of pesticide
It loses, improves the effective rate of utilization and drug effect of pesticide；Further, the medicine-carried system of nanoscale makes pesticide and pest target
Contact area increases, and can increase pesticide to the insecticidal activity of pest target.Alkyd resin/pesticide nano emulsion dispersibility is good,
Lotion can store 12 months or more.Up to 50%, encapsulation rate is not less than alkyd resin/pesticide nano emulsion carriers drugloading rate
90%, and emulsion solid content and drugloading rate can be adjusted according to actual needs, it has wide range of applications.Alkyd resin/pesticide nano cream
Liquid has medicine sustained and controlled release performance, can maintain longer administration time, reduces administration number of times and dosage, to improve biological benefit
With rate, pesticide cost is reduced.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Latex particle size in following embodiments in Malvern company, Britain Zetasizer 3000HSA laser particle size and
It is measured at 25 DEG C in potentiometric analyzer.
Alkyd resin/pesticide nano lotion drugloading rate and encapsulation rate are to utilize Beijing Pu Xi all purpose instrument Co., Ltd T6
Ultraviolet-uisible spectrophotometer measurement, specific assay method is as follows: taking appropriate alkyd resin/pesticide nano lotion and a small amount of cycloalkanes
Sour cobalt lotion mixes, and the cobalt content in cobalt naphthenate is the 0.1% of alkyd resin quality, and drying and forming-film at room temperature.Then
The latex film for weighing certain mass is soaked in a certain amount of cyclohexane solvent, passes through ultraviolet-uisible spectrophotometer after ultrasound
Measure pesticide concentration.
Drugloading rate and encapsulation rate calculation formula are as follows:
Drug quality/latex film quality × 100% in drugloading rate (%)=latex film；
Encapsulation rate (%)=(quality of the emulsion obtained × practical solid content × practical drugloading rate)/offerd medicine amount of substance ×
100%.
Embodiment 1: alkyd resin/lambda-cyhalothrin nanoemulsion liquid
(a) preparation of alkyd resin carrier: it is 50% that vegetable oil, which accounts for the mass fraction of resin Theoretical Mass, in component design,
The ratio between original-OH integral molar quantity and-COOH integral molar quantity are 1.2 in reactant.By 527g linseed oil, 263g trimethylolpropane
It is added in four-hole bottle, 180 DEG C is warming up under the stirring condition of 300r/min；Then 249g M-phthalic acid is added to four
In mouth bottle, it is continuously heating to 235 DEG C and carries out under nitrogen protection esterification 2 hours, constantly separate water during the reaction,
The acid value of reactant enters in next step when being 8.6mgKOH/g；150 DEG C are cooled to, 102g trimellitic anhydride is added, is warming up to 178
DEG C the reaction was continued 1 hour, and reactant acid value is constantly measured in reaction process, stops reaction when acid value reaches 56.4mgKOH/g,
Obtain alkyd resin.
(b) high speed in situ phase reversal carrying medicament: (1) taking 10.1g alkyd resin in there-necked flask, is added at 60 DEG C
The mixing of 1.03g triethylamine obtains waterborne alkyd resin so that system is neutrality；(2) 9.2g gamma cyhalothrin is dissolved in
In 8mL ethyl acetate, the pesticide solution is obtained；(3) at 60 DEG C, it is equal that mixing is added into waterborne alkyd resin in the pesticide solution
It is even, 0.05g SDBS and 0.1g TX-10 are dissolved in 35mL deionized water and obtain emulsifier solution, and will be newborn at 60 DEG C
Agent solution is added into the pesticide solution and waterborne alkyd resin mixed solution, and the high speed under the stirring condition of 1800r/min
Phase reversal in situ, so that system emulsification is uniformly, vacuum distillation removes ethyl acetate at 40 DEG C, obtains alkyd resin/efficient chlorine
Flucythrinate nanoemulsions, transmission electron microscope figure are as shown in Figure 2.
Gained alkyd resin/lambda-cyhalothrin nanoemulsion liquid quality solid content is 37.5wt%, averagely hydration grain
Diameter is 54.9nm, and carrier is 45.7% to the drugloading rate of gamma cyhalothrin, encapsulation rate 91.4%.
Embodiment 2: alkyd resin/lambda-cyhalothrin nanoemulsion liquid
(a) preparation of alkyd resin carrier: it is 60% that vegetable oil, which accounts for the mass fraction of resin Theoretical Mass, in component design,
The ratio between original-OH integral molar quantity and-COOH integral molar quantity are 1.2 in reactant.644g soya-bean oil, 140g glycerol are added to four mouthfuls
In bottle, 180 DEG C are warming up under the stirring condition of 300r/min；Then 55.4g M-phthalic acid is added into four-hole bottle,
It is carried out under nitrogen protection esterification 1 hour, water is constantly separated during the reaction, when the acid value of reactant is 8.2mgKOH/g
Into in next step；150 DEG C are cooled to, 188g trimellitic anhydride is added, is warming up to 178 DEG C and continues the reaction for 40 minutes, reaction process
In constantly measure reactant acid value, when acid value reaches 66.7mgKOH/g stop reaction, obtain alkyd resin.
(b) high speed in situ phase reversal carrying medicament: (1) taking 10.4g alkyd resin in there-necked flask, is added at 60 DEG C
The mixing of 1.25g triethylamine obtains waterborne alkyd resin so that system is neutrality；(2) 7.9g gamma cyhalothrin is dissolved in
In 8mL ethyl acetate, the pesticide solution is obtained；(3) at 60 DEG C, it is equal that mixing is added into waterborne alkyd resin in the pesticide solution
It is even；0.05g SDS and 0.1g OP-10 are dissolved in 37mL deionized water and obtain emulsifier solution, and will emulsification at 60 DEG C
Agent solution is added into the pesticide solution and waterborne alkyd resin mixed solution, and the high speed in situ under 2000r/min stirring condition
Phase reversal, so that system emulsification is uniformly, vacuum distillation removes ethyl acetate at 40 DEG C, obtains alkyd resin/efficient chlorine fluorine cyanogen
Pyrethroids nanoemulsions.
Gained alkyd resin/lambda-cyhalothrin nanoemulsion liquid quality solid content is 35.6wt%, averagely hydration grain
Diameter is 35.1nm, and carrier is 40.7% to the drugloading rate of gamma cyhalothrin, encapsulation rate 92.5%.
Embodiment 3: alkyd resin/lambda-cyhalothrin nanoemulsion liquid
(a) preparation of alkyd resin carrier: it is 50% that vegetable oil, which accounts for the mass fraction of resin Theoretical Mass, in component design,
The ratio between original-OH integral molar quantity and-COOH integral molar quantity are 1.15 in reactant.By 457.5g tung oil, 203.7g trihydroxy methyl
Propane is added in four-hole bottle, and 180 DEG C are warming up under the stirring condition of 300r/min；Then 166.1g M-phthalic acid is added
Enter into four-hole bottle, carries out under nitrogen protection esterification 1.5 hours, constantly separate water during the reaction, reactant
Acid value enters in next step when being 7.8mgKOH/g；150 DEG C are cooled to, 188g trimellitic anhydride is added, 178 DEG C is warming up to and continues instead
It answers 1.5 hours, reactant acid value is constantly measured in reaction process, stop reaction when acid value reaches 46.7mgKOH/g, obtain alcohol
Acid resin.
(b) high speed in situ phase reversal carrying medicament: (1) taking 11.2g alkyd resin in there-necked flask, is added at 70 DEG C
The mixing of 0.95g triethylamine obtains waterborne alkyd resin so that system is neutrality；(2) 5.2g gamma cyhalothrin is dissolved in
In 10mL ethyl alcohol, the pesticide solution is obtained；(3) at 70 DEG C, the pesticide solution is added into waterborne alkyd resin and is uniformly mixed, it will
40mL deionized water is added into the pesticide solution and waterborne alkyd resin mixed solution at 70 DEG C, and is stirred in 1500r/min
Under the conditions of high speed in situ phase reversal so that system emulsification uniformly, at 45 DEG C vacuum distillation remove ethyl alcohol, obtain alkyd resin/
Lambda-cyhalothrin nanoemulsion liquid.
Gained alkyd resin/lambda-cyhalothrin nanoemulsion liquid quality solid content is 31.1wt%, averagely hydration grain
Diameter is 110.8nm, and carrier is 30.7% to the drugloading rate of gamma cyhalothrin, encapsulation rate 96.1%.
Embodiment 4: alkyd resin/avermectin nanometer lotion
(a) preparation of alkyd resin carrier: with embodiment 1.
(b) high speed in situ phase reversal carrying medicament: (1) taking 10.9g alkyd resin in there-necked flask, is added at 70 DEG C
The mixing of 1.11g triethylamine obtains waterborne alkyd resin so that system is neutrality；(2) 1.2g avermectin is dissolved in 15mL second
In alcohol, the pesticide solution is obtained；(3) at 70 DEG C, the pesticide solution is added into waterborne alkyd resin and is uniformly mixed, by 0.05g
SDBS and 0.11g TX-10, which is dissolved into 38mL deionized water, obtains emulsifier solution, and adds emulsifier solution at 70 DEG C
Enter into the pesticide solution and waterborne alkyd resin mixed solution, the high speed in situ phase reversal under 1400r/min stirring condition, so that
Uniformly, vacuum distillation removes ethyl alcohol at 45 DEG C for system emulsification, obtains alkyd resin/avermectin nanometer lotion.
Gained alkyd resin/avermectin nanometer lotion quality solid content is 27.2wt%, and averagely hydration partial size is
147.2nm, carrier are 10.1% to the drugloading rate of avermectin, encapsulation rate 93.5%.
Embodiment 5: alkyd resin/avermectin nanometer lotion
(a) preparation of alkyd resin carrier: with embodiment 2.
(b) high speed in situ phase reversal carrying medicament: (1) taking 10.2g alkyd resin in there-necked flask, is added at 50 DEG C
The mixing of 1.23g triethylamine obtains waterborne alkyd resin so that system is neutrality；(2) 2.8g avermectin is dissolved in 10mL third
In ketone, the pesticide solution is obtained；(3) at 50 DEG C, the pesticide solution is added into waterborne alkyd resin and is uniformly mixed, by 0.05g
SDS and 0.1g OP-10, which is dissolved into 36mL deionized water, obtains emulsifier solution, and emulsifier solution is added at 50 DEG C
Into the pesticide solution and waterborne alkyd resin mixed solution, and the high speed in situ phase reversal under the stirring condition of 1200r/min, make
Uniformly, vacuum distillation removes acetone at 40 DEG C for the system emulsification of obtaining, and obtains alkyd resin/avermectin nanometer lotion.
Gained alkyd resin/avermectin nanometer lotion quality solid content is 28.9wt%, and averagely hydration partial size is
181.9nm, carrier are 20.2% to the drugloading rate of avermectin, encapsulation rate 91.0%.
Embodiment 6: alkyd resin/avermectin nanometer lotion
(a) preparation of alkyd resin carrier: with embodiment 3.
(b) high speed in situ phase reversal carrying medicament: (1) taking 11g alkyd resin in there-necked flask, is added at 50 DEG C
The mixing of 0.93g triethylamine obtains waterborne alkyd resin so that system is neutrality；(2) 4g avermectin is dissolved in 15mL acetone
In, obtain the pesticide solution；(3) at 50 DEG C, by the pesticide solution be added into waterborne alkyd resin be uniformly mixed, by 39mL go from
Sub- water is added into the pesticide solution and waterborne alkyd resin mixed solution at 50 DEG C, the high speed under 1000r/min stirring condition
Phase reversal in situ, so that system emulsification is uniformly, vacuum distillation removes acetone at 40 DEG C, obtains alkyd resin/avermectin and receives
Rice milk liquid.
Gained alkyd resin/avermectin nanometer lotion quality solid content is 30.2wt%, and averagely hydration partial size is
217.5nm, carrier are 25.7% to the drugloading rate of avermectin, encapsulation rate 95.6%.
Embodiment 7: alkyd resin/phoxim nanoemulsions
(a) preparation of alkyd resin carrier: with embodiment 1.
(b) high speed in situ phase reversal carrying medicament: (1) taking 10.8g alkyd resin in there-necked flask, is added at 70 DEG C
The mixing of 1.11g triethylamine obtains waterborne alkyd resin so that system is neutrality；(2) 8.1g phoxim is dissolved in 10mL isopropyl
In alcohol, the pesticide solution is obtained；(3) at 70 DEG C, the pesticide solution is added into waterborne alkyd resin and is uniformly mixed, by 0.05g
SDBS and 0.11g TX-10, which is dissolved into 38mL deionized water, obtains emulsifier solution, and adds emulsifier solution at 70 DEG C
Enter into the pesticide solution and waterborne alkyd resin mixed solution, the high speed in situ phase reversal under 1600r/min stirring condition, so that
Uniformly, vacuum distillation removes isopropanol at 45 DEG C for system emulsification, obtains alkyd resin/phoxim nanoemulsions.
Gained alkyd resin/phoxim nanoemulsions quality solid content is 35.7wt%, and averagely hydration partial size is
87.7nm, carrier are 41.1% to the drugloading rate of phoxim, encapsulation rate 90.5%.
Embodiment 8: alkyd resin/phoxim nanoemulsions
(a) preparation of alkyd resin carrier: with embodiment 2.
(b) high speed in situ phase reversal carrying medicament: (1) taking 9.9g alkyd resin in there-necked flask, is added at 60 DEG C
The mixing of 1.19g triethylamine obtains waterborne alkyd resin so that system is neutrality；(2) by 4.8g phoxim be dissolved in 8mL just oneself
In alkane, the pesticide solution is obtained；(3) at 60 DEG C, the pesticide solution is added into waterborne alkyd resin and is uniformly mixed, by 0.05g
SDS and 0.1g OP-10, which is dissolved into 35mL deionized water, obtains emulsifier solution, and emulsifier solution is added at 60 DEG C
Into the pesticide solution and waterborne alkyd resin mixed solution, the high speed in situ phase reversal under 1700r/min stirring condition, it is proper to make
Uniformly, vacuum distillation removes n-hexane to system's emulsification at 50 DEG C, obtains alkyd resin/phoxim nanoemulsions.
Gained alkyd resin/phoxim nanoemulsions quality solid content is 32.2wt%, and averagely hydration partial size is
63.9nm, carrier are 30.7% to the drugloading rate of phoxim, encapsulation rate 95.4%.
Embodiment 9: alkyd resin/phoxim nanoemulsions
(a) preparation of alkyd resin carrier: with embodiment 3.
(b) high speed in situ phase reversal carrying medicament: (1) taking 13.1g alkyd resin in there-necked flask, is added at 50 DEG C
The mixing of 1.1g triethylamine obtains waterborne alkyd resin so that system is neutrality；(2) 10.3g phoxim is dissolved in 8mL acetone
In, obtain the pesticide solution；(3) at 50 DEG C, by the pesticide solution be added into waterborne alkyd resin be uniformly mixed, by 46mL go from
Sub- water is added into the pesticide solution and waterborne alkyd resin mixed solution at 50 DEG C, the high speed under 1500r/min stirring condition
Phase reversal in situ, so that system emulsification is uniformly, vacuum distillation removes acetone at 40 DEG C, obtains alkyd resin/phoxim nanometer
Lotion.
Gained alkyd resin/phoxim nanoemulsions quality solid content is 35.5wt%, and averagely hydration partial size is
105.1nm, carrier are 43.9% to the drugloading rate of phoxim, encapsulation rate 94.0%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of alkyd resin/pesticide nano lotion characterized by comprising water-insoluble pesticide, alkyd resin and water.
2. alkyd resin according to claim 1/pesticide nano lotion, which is characterized in that the water-insoluble pesticide, institute
The mass ratio for stating alkyd resin and the water is 0.01~25:9.99~49.99:50~90.
3. alkyd resin according to claim 1 or 2/pesticide nano lotion, which is characterized in that the alkyd resin is
Vegetable oil and polyalcohol, binary acid or acid anhydrides, containing there are three and above functional group's polyacid or acid anhydrides is aggregated reacts；
It is optional, the vegetable oil and the polyalcohol, the binary acid or acid anhydrides, it is described containing there are three and the above functional group it is more
The mass ratio of first acid or acid anhydrides is 10:2~9:0.5~9.5:1.5~3；
It is optional, the vegetable oil, the polyalcohol, the binary acid or acid anhydrides, it is described containing there are three and the above functional group it is more
First acid or the ratio between the-OH integral molar quantity in acid anhydrides and-COOH integral molar quantity are 1.1~1.4；
Optional, the acid value of the alkyd resin is 35~70mgKOH/g.
4. alkyd resin according to claim 3/pesticide nano lotion, which is characterized in that the vegetable oil is selected from Asia
At least one of sesame oil, soya-bean oil, tung oil, castor oil, coconut oil and cottonseed oil；
Optional, the polyalcohol is selected from glycerol, pentaerythrite, trimethylolpropane, trimethylolethane, ethylene glycol, third
At least one of glycol, butanediol and neopentyl glycol；
Optional, the binary acid or acid anhydrides are selected from M-phthalic acid, phthalic anhydride, terephthalic acid (TPA), maleic two
At least one of formic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride；
It is optional, it is described containing there are three and above functional group's polyacid or acid anhydrides for selected from trimellitic anhydride, pyromellitic dianhydride
At least one of.
5. alkyd resin according to claim 1 or 2/pesticide nano lotion, which is characterized in that the water-insoluble pesticide
For selected from gamma cyhalothrin, cyfloxylate, Biphenthrin, decis, fenvalerate, thiacloprid, clothianidin, triazole
Phosphorus, carbosulfan, avermectin, acetylamino evericin, ivermectin, chlorine pyrazothion, phoxim, Rynaxypyr
At least one of；
It is optional, the water-insoluble pesticide be selected from gamma cyhalothrin, cyfloxylate, avermectin, ivermectin,
At least one of chlorine pyrazothion and phoxim.
6. a kind of prepare alkyd resin of any of claims 1-5/pesticide nano lotion method, feature exists
In, comprising:
(1) alkyd resin is mixed into neutralization with lye, to obtain waterborne alkyd resin；
(2) water-insoluble pesticide is mixed with cosolvent, to obtain the pesticide solution；
(3) waterborne alkyd resin, the pesticide solution and emulsifier solution/water are mixed, and is steamed through phase reversal and decompression
Processing is evaporated, to obtain alkyd resin/pesticide nano lotion.
7. according to the method described in claim 6, it is characterized in that, the lye is selected from organic base or nothing in step (1)
At least one of machine alkali；
Optional, the organic base is selected from least one of triethylamine, trimethylamine；
Optional, the inorganic base is selected from least one of ammonium hydroxide and sodium hydroxide；
Optional, in step (1), the mass ratio of the alkyd resin and the lye is 10:0.5~1.5.
8. method according to claim 6 or 7, which is characterized in that in step (2), the cosolvent is selected from acetic acid
At least one of ethyl ester, ethyl alcohol, methanol, isopropanol, acetone, butanone, hexamethylene and n-hexane；
Optional, in step (2), the boiling point of the cosolvent is 50~100 DEG C；
Optional, in step (2), the mass ratio of the water-insoluble pesticide and the cosolvent is 1:0.5~2.
9. according to the method described in claim 6, it is characterized in that, the emulsifier includes anionic emulsifying in step (3)
Agent and nonionic emulsifier；
It is optional, in step (3), the anion emulsifier be in alkyl sulfate and alkylbenzene sulfonate at least
One of；
Optional, in step (3), the nonionic emulsifier is selected from alkyl phenol polyoxyethylene ether class, Tweens and this disk
At least one of class；
Optionally, in step (3), in the emulsifier solution quality of emulsifier be the alkyd resin quality 0~
3%；
Optional, in step (3), the waterborne alkyd resin, the pesticide solution and the emulsifier solution/water
Mass ratio is 9.99~49.99:0.02~60:50~91.5.
10. according to the method described in claim 6, it is characterized in that, in step (3), the mixing speed of the phase reversal is
1000~2000r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910363551.7A CN109997847B (en) | 2019-04-30 | 2019-04-30 | Alkyd resin/pesticide nano emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910363551.7A CN109997847B (en) | 2019-04-30 | 2019-04-30 | Alkyd resin/pesticide nano emulsion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109997847A true CN109997847A (en) | 2019-07-12 |
| CN109997847B CN109997847B (en) | 2021-05-04 |
Family
ID=67175532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910363551.7A Active CN109997847B (en) | 2019-04-30 | 2019-04-30 | Alkyd resin/pesticide nano emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109997847B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111345291A (en) * | 2020-04-15 | 2020-06-30 | 扬州大学 | Avermectin nano emulsion and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1136034A (en) * | 1966-09-13 | 1968-12-11 | Walpamur Company Ltd | Improvements in or relating to pesticidal film-forming compositions |
| CN101361476A (en) * | 2008-09-24 | 2009-02-11 | 四川省兰月农化科技开发有限责任公司 | Multiple-effect azole microcapsule suspension formulation with slow-release function and preparation method thereof |
| CN105052902A (en) * | 2015-08-04 | 2015-11-18 | 清华大学 | Sustained and controlled release pesticide nanometer emulsion and preparation method thereof |
| CN107853299A (en) * | 2017-12-03 | 2018-03-30 | 中国农业科学院农业环境与可持续发展研究所 | A kind of blade face affinity type pesticide nano drug-loading system preparation method |
-
2019
- 2019-04-30 CN CN201910363551.7A patent/CN109997847B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1136034A (en) * | 1966-09-13 | 1968-12-11 | Walpamur Company Ltd | Improvements in or relating to pesticidal film-forming compositions |
| CN101361476A (en) * | 2008-09-24 | 2009-02-11 | 四川省兰月农化科技开发有限责任公司 | Multiple-effect azole microcapsule suspension formulation with slow-release function and preparation method thereof |
| CN105052902A (en) * | 2015-08-04 | 2015-11-18 | 清华大学 | Sustained and controlled release pesticide nanometer emulsion and preparation method thereof |
| CN107853299A (en) * | 2017-12-03 | 2018-03-30 | 中国农业科学院农业环境与可持续发展研究所 | A kind of blade face affinity type pesticide nano drug-loading system preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 杨涛: "水性醇酸树脂的合成及改性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111345291A (en) * | 2020-04-15 | 2020-06-30 | 扬州大学 | Avermectin nano emulsion and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109997847B (en) | 2021-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20210007996A1 (en) | Method for preparing particles comprising metal oxide coating and particles with metal oxide coating | |
| CN110946133B (en) | Nano photolysis-resistant controlled-release pesticide with lignin as coating matrix and preparation method thereof | |
| CN102112219A (en) | Microcapsules comprising active ingredients and metal oxide shell, method for their preparation and uses thereof | |
| CN105052902B (en) | Slow controlled release pesticide nano emulsion and preparation method thereof | |
| CN107279174B (en) | Preparation method of efficient cyhalothrin nano pesticide | |
| CN111620964B (en) | Compound essential oil microcapsule preparation for preventing and treating banana wilt and preparation method thereof | |
| WO2018209293A2 (en) | Nanoscale multiple emulsions and nanoparticles | |
| CN107455492A (en) | A kind of method that nano-silicon dioxide modified microcapsule wall material prepares microcapsules | |
| CN104886091B (en) | A kind of biodegradable emamectin-benzoate microballoon | |
| WO2021068270A1 (en) | Nano aqueous formulation comprising chlorpyrifos and preparation method thereof | |
| CN106810800A (en) | A kind of preparation method of antibiotic property polyvinyl alcohol/cellulose oxidation Graphene PVA/CNC GO composite membranes | |
| CN109997847A (en) | Alkyd resin/pesticide nano lotion and preparation method thereof | |
| CN108094421A (en) | It is a kind of using biodegradable material as the preparation method of the pesticide microballoon of support materials | |
| CN113575243A (en) | Liquid fruit bagging material, preparation method and application thereof | |
| KR20070059074A (en) | Romp polymer particles comprising active ingredients | |
| CA3074131A1 (en) | Essential oil microparticles for powder coating applications | |
| CN106332876A (en) | Pyrethroid-pesticide-containing emulsion in water and preparation method thereof | |
| CN105997876A (en) | Preparation method of resveratrol liposome modified with food-grade chitosan | |
| US11363813B2 (en) | Hydrogels as rheology modifiers and methods of making the same | |
| CN103828801B (en) | Pleocidin/emamectin-benzoate microballoon and preparation method thereof | |
| CN101606519A (en) | The disinfectant use in agriculture that contains allicin | |
| CN101926357A (en) | Hot fogging concentrate of binary composition containing emamectin benzoate and dursban, and preparing method thereof | |
| JP2021049487A (en) | Controlled-release composite particle and method for producing the same and dry powder using the particle | |
| Cheng et al. | Optimization of multifunctional polymer emulsifiers properties for lambda-cyhalothrin nanoemulsion fabrication | |
| CN114190374B (en) | Microcapsule suspension preparation, microcapsule suspension seed coating agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |