CN109362723A - A kind of load pesticide lignin microcapsules and preparation method thereof based on emulsion interface crosslinking - Google Patents
A kind of load pesticide lignin microcapsules and preparation method thereof based on emulsion interface crosslinking Download PDFInfo
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- CN109362723A CN109362723A CN201811452189.2A CN201811452189A CN109362723A CN 109362723 A CN109362723 A CN 109362723A CN 201811452189 A CN201811452189 A CN 201811452189A CN 109362723 A CN109362723 A CN 109362723A
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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
- A01N25/26—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 in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
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Abstract
The invention belongs to pesticide micro capsule preparation technical fields, disclose a kind of load pesticide lignin microcapsules and preparation method thereof based on emulsion interface crosslinking.Preparation method of the present invention first uses Mannich method to prepare aminated lignin, then alkali-soluble acid analysis prepares aminated lignin particle dispersion in water, crosslinking agent is added, as water phase；Pesticide and organic solvent are mixed as oily phase；Water phase and oil are mixed, emulsified, O/W type Pickering lotion is prepared；Catalyst is added, heat cross-linking reaction obtains carrying pesticide lignin microcapsules.The present invention also provides the load pesticide lignin microcapsules of above method preparation, and using the lignin from industrial by-products as one of the raw material of synthesis microcapsule wall material, cyst material is at low cost, degradable；Cyst wall compact structure can effectively delay the release of pesticide active ingredient, and contain a large amount of hindered phenol structures in lignin molecule, be also beneficial to further increase the photostability of the enhancing quick pesticide of photosensitive or oxygen.
Description
Technical field
The invention belongs to pesticide micro capsule preparation technical field, in particular to a kind of load pesticide based on emulsion interface crosslinking
Lignin microcapsules and preparation method thereof.
Background technique
China is every year because direct economic loss is up to 10,000,000,000 yuan caused by pest and disease damage, in order to guarantee grain good harvest and agricultural development,
It needs largely to use pesticide.But pesticide poisoning and pollution problem are paid more and more attention, and pesticidal preparations are gradually to safety, low toxicity, height
The greenization direction of effect is developed.Pesticide micro capsule is that raw medicine is wrapped up and is fixed up with cyst material, is formed with certain cladding
The semi-permeable membrane capsule of intensity.Since effective component is wrapped by, toxicity is both reduced, in turn avoids degradation in the environment, and can
Slow release improves pesticide utilization rate, reduces medication, reduces environmental pressure, agree with pesticide greenization requirement.
The wall material of pesticide micro capsule has very much, at present common synthesis high molecular material or natural macromolecular material.Synthesis is high
Molecular material includes polyureas, Lauxite etc., passes through emulsion polymerization encystation；Natural macromolecular material mainly has gelatin, Arab
Glue etc., frequently with physico-chemical process encystation such as multiple cohesions.But synthesis high score ascus wall too closely causes pesticide active ingredient to be difficult to release
It puts, and monomer toxicity is big, pollution environment；Natural polymer ascus wall film-strength is low, slow release effect is poor.Particularly with easy photodissociation, easily
The biological pesticide and botanical pesticide of oxidative degradation, the above two equal protectiveness of wall material is insufficient.
Lignin is the aromatic polymer for one kind complexity being present in plant, and reserves in nature are only second to
Cellulose, paper-making pulping industry in China's is annual about to generate 20,000,000 tons of industrial lignins.By lignin in pesticide micro capsule wall material
Middle application has the advantage that (1) industrial lignin is cheap, helps to reduce microcapsules preparation cost；And its is nontoxic, can
Biodegrade, catabolite have fertilizer efficiency to crops；(2) contain a large amount of phenyl ring, conjugated structure in lignin molecule and can have
Effect remove free radical phenolic hydroxyl group, have good thermal stability, UV absorption and antioxygenic property, can significantly increase it is photosensitive or
The chemical stability of the quick pesticide of oxygen；(3) lignin molecule is in three-dimensional net structure, has certain envelope and infiltration to pesticide
Property, facilitate the sustained release rate for adjusting effect microcapsule wall.Therefore, pesticide micro capsule is prepared by wall material of lignin, it not only can be real
Existing Liginon Resourceization utilizes, and can also solve the bottleneck problems such as microcapsules controlled release and anti-photolysis performance difference, pushes pesticide micro capsule
Large-scale application.
Two are concentrated on using the research that lignin prepares pesticide (mainly Photosensitive pesticide avermectin) microcapsules at present
Aspect: (1) with other macromolecules are compound prepares compound wall materials microcapsules.Such as pay for gold using emulsion polymerization be prepared for it is wooden
Plain phenolic aldehyde base [polymer material science and engineering [J], 2012,28 (10): 117-120.] and lignin urea aldehyde radical carry Avermectin
Plain microcapsules [Chinese patent [P] .:CN 102349509 B, 2013.07.31]；All refined equal [all refined LBL self-assembly preparation loads
Medicine chitosan/sodium lignin sulfonate microcapsules and its Beijing drug release behavior [D]: Beijing University of Chemical Technology, 2008] with sulfomethylated lignin
Sour sodium and chitosan are wall material, are prepared for avermectin microcapsule using layer-by-layer；[Beijing chemical industry is big by Ma Lijie etc.
Learn journal (natural science edition) [J], 2006,33 (6): 51-56] using chitosan and sodium lignin sulfonate as wall material, using coagulating again
Poly- method prepares avermectin microcapsule；The particle-stabilised Pickering of present inventor [201710023899.2] lignin
Lotion is template, prepares lignin/polyureas composite micro-capsule for encapsulating avermectin, cyhalothrin and chlopyrifos etc..
(2) Vinsol's wall material microcapsules.Li et al. [Acs Sustainable Chemistry&Engineering,
2017,5 (4): 3321-3328] utilize electrostatic self-assembled method by sodium lignin sulfonate (SL) and cetyl trimethylammonium bromide
CTAB assembling, and encapsulating is carried out to avermectin and prepares the drug bearing microsphere with hydrophobicity wall material SL-CTAB；Xu Ruilin preparation
Amido sodium lignin sulfonate with pH responsiveness, prepares avermectin microcapsule using complex coacervation；Deng
[Industrial Crops&Products, 2016,87191-197] etc. is modified preparation wood to alkali lignin using aniline
Quality base azobenzene polymer, then by it in THF/H2The characteristic that hollow colloidal spheres can be self-assembly of in O mixed liquor is come
Preparation encloses the lignin-base azobenzene polymer colloidal spheres of avermectin.
Therefore Vinsol's load pesticide micro capsule uses physical-chemical process to prepare substantially at present, when preparing microcapsules
It needs using relative complex process conditions and cumbersome operation, it is difficult to realize industrialization.Emulsion polymerization or crosslinking are in industry
Preparation synthesis macromolecule wall material carries the common and mature method of pesticide micro capsule, and Vinsol carries the preparation of pesticide micro capsule
It should develop toward this direction.There are research and utilization lignin sulfonic acid saline solution and crosslinking agent (such as toluene di-isocyanate(TDI) [Rsc
Advances 2014；4:11661-11663], epoxychloropropane [Soft Matter, 2015,11,2046-2054], 3- sulfydryl
Propionic ester [ACS Sustainable Chemistry&Engineering (2016), 4 (10), 5204-5211] etc.) in emulsion droplet
Interface crosslinks preparation Vinsol and receives/microcapsules, is used for encapsulating hydrophilic or lyophobic dust.But due to lignin sulfonic acid
Salt diffuses to emulsion droplet interface from water phase and could participate in reacting, and leads to low crosslinking degree, thin cyst, intensity difference, fragile.Therefore, have
Necessity develops a kind of load pesticide lignin wall material microcapsules based on emulsion polymerization or crosslinking, with fine and close cyst wall structure.
Summary of the invention
In order to overcome, above-mentioned prior art processes complex operations are cumbersome, it is micro- to prepare lignin using emulsion polymerization or cross-linking method
The disadvantage and deficiency that capsule wall material intensity is low, stability is poor, the primary purpose of the present invention is that providing a kind of based on emulsion interface
The preparation method of the load pesticide lignin microcapsules of crosslinking.
The lignin particle for being largely adsorbed on emulsion interface is cross-linked to form continuous wood using crosslinking agent by the method for the present invention
Quality cyst wall prepares cyst wall intensity higher lignin wall material microcapsules under the conditions of comparatively gentle, using straightforward procedure, at
Function overcomes the deficiency of above-mentioned technology.Specially the dispersion of lignin particle is prepared first with the characteristic of lignin alkali-soluble acid analysis
Liquid；Then oily phase is formed with pesticide and organic solvent, crosslinking agent is added in lignin particle dispersion and forms water phase, by water phase and
Oil prepares O/W type Pickering lotion after mixing, emulsifying, and lignin particle high density is made to be adsorbed on oil-water interfaces；Then plus
Enter catalyst, at a certain temperature, causes lignin particles and crosslinking agent crosslinks polymerization reaction at oil-water interfaces, formed
Carry pesticide lignin microcapsules.In order to improve the reactivity of lignin and crosslinking agent, lignin particle water dispersion liquid is being prepared
It is preceding that amination modifying is carried out to it using Mannich method, it is grafted to organic amine group on lignin molecule.
Another object of the present invention is to provide the load pesticide lignin wall material microcapsules of above method preparation.
The purpose of the present invention is realized by following proposal:
A kind of preparation method of the load pesticide lignin microcapsules based on emulsion interface crosslinking, is first prepared using Mannich method
Aminated lignin, then alkali-soluble acid analysis prepares aminated lignin particle dispersion in water, crosslinking agent is added, as water phase；By agriculture
Medicine and organic solvent mixing are as oily phase；Water phase and oil are mixed, emulsified, O/W type Pickering lotion is prepared；Addition is urged
Agent, heat cross-linking reaction obtain carrying pesticide lignin microcapsules.
Dosage of each component is preferably mass parts: 100 parts of water；1~10 part of aminated lignin；0.4~10 part of crosslinking agent；Agriculture
0.1~12 part of medicine；10~60 parts of organic solvent；0.01~0.1 part of catalyst.
It is described that Mannich method is used to prepare aminated lignin as conventional method, it can be such as prepared by including the following steps
To: lignin is dissolved in 9~12 lye of pH, aminating agent, formalin is added, heating reaction obtains aminated lignin.
Lignin used, aminating agent, formaldehyde mass ratio be preferably 10:(10~20): (47~95).
3~5h is preferably reacted in the heating reaction at 70~90 DEG C.
The concentration that the lignin is dissolved in 9~12 lye of pH is preferably 20~40wt%.
The concentration of the formalin is preferably 37wt%.
The aminating agent may include at least one of ethylenediamine, hexamethylene diamine and diethylenetriamines.
The lignin may include at least one of alkali lignin and enzymolysis xylogen, preferably two of them.
Further preferably to realize the object of the invention, the alkali lignin can be selected from pulp black liquor, bamboo pulp black liquor, wheat
One of straw pulp black liquor, reed pulp black liquor, bagasse black liquor, Dracaena straw pulp black liquor, cotton stalk pulp black liquor and cotton pulp black liquor, warp
Lignin by acid separation powder after crossing acid out drying.The enzymolysis xylogen may include plant material (corn stover, corncob
Deng) in cellulose fermentation prepare the lignin of separation and Extraction in the residue of alcohol.
After the heating reaction aminated lignin can be obtained by the way that revolving is dry.
In preparation method of the present invention, the crosslinking agent may include glutaraldehyde, dihydroxymethyl ethylene urea, citric acid, 1,2,
At least one of 3,4- butane tetracarboxylic acid, ethylene glycol diglycidylether.
The pesticide is fat-soluble pesticide, it may include at least one of avermectin, cyhalothrin and chlopyrifos etc..
The organic solvent may include one of toluene, cyclohexanone and isophorone.
The catalyst may include at least one of sodium hypophosphite, zinc nitrate and sodium chloride.
The emulsification is preferably in 5~20min of the emulsified processing of 8000~13000rpm.
1~8h is preferably reacted in the heat cross-linking reaction at the mixing speed of 50~300rpm, 50~80 DEG C.
In preparation method of the present invention, alkali-soluble acid analysis prepares aminated lignin particle dispersion to aminated lignin in water, refers to
Aminated lignin is dissolved in lye, acid is added, lignin is made to be precipitated to form aminated lignin particle dispersion.
The alkali may include at least one of sodium hydroxide, potassium hydroxide, ammonium hydroxide.
The acid may include at least one of hydrochloric acid, sulfuric acid, nitric acid.
More specifically aminated lignin is added to the water, it is 9~12 that alkali, which is added, and adjusts pH, aminated lignin solution is obtained,
Adding sour regulation system pH is 4~6, and aminated lignin is made to be precipitated to form aminated lignin particle dispersion.The amination wood
Quality solution can be filtered, and carry out acid out again after removing undissolved lignin.
Preparation method of the present invention specifically includes the following steps:
(1) preparation of aminated lignin particle dispersion: being added to the water aminated lignin, and it is 9 that alkali, which is added, and adjusts pH
~12, aminated lignin solution is obtained, filtrate is filtered to take, adding acid to pH is 4~6, obtains the dispersion of aminated lignin particle
Liquid；
(2) prepared by Pickering lotion: crosslinking agent is added as water phase, by pesticide in aminated lignin particle dispersion
It is dissolved in organic solvent as oily phase, after water-oil phase mixing, emulsification obtains the particle-stabilised oil-in-water of lignin (O/W) type
Pickering lotion；
(3) it carries the synthesis of pesticide lignin microcapsules: catalyst being added into lotion, heat cross-linking reaction obtains carrying agriculture
Medicine lignin microcapsule suspensions.
The load pesticide lignin microcapsule suspensions that preparation method of the present invention is prepared are dried, can be obtained load
Pesticide lignin microcapsules.
The present invention also provides the load pesticide lignin microcapsules of above method preparation, cyst material is at low cost, degradable；Capsule
Wall construction densification can effectively delay the release of pesticide active ingredient, and lignin molecule contains a large amount of hindered phenol structures, can improve
Enhance the photostability of the quick pesticide of photosensitive or oxygen.
Preparation method simple process of the present invention, reaction condition are mild.Preparation method of the present invention is to derive from industrial by-products
Raw material one of of the lignin as synthesis microcapsule wall material, be effectively reduced the production cost of microcapsules, realize abandoned biomass
Resource utilization, reduce the cost of microcapsules；Simultaneously because lignin is degradable, lignin does the microcapsules of wall material certainly
Right boundary can slowly degrade, environmental-friendly；And contains a large amount of hindered phenol structures in lignin molecule, be also beneficial to further increase
Enhance the photostability of the quick pesticide of photosensitive or oxygen.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
1, the method for the present invention first prepares aminated lignin particle, and using it as solid dispersed particle, prepares O/W
Pickering lotion, makes aminated lignin be adsorbed on oil-water interfaces, directly hands over so as to the crosslinking agent preferably with water phase
Connection reaction participates in the content of lignin height that wall material is formed, and the cyst wall of preparation is thicker and intensity is high.
2, in the method for the present invention, in order to improve the reactivity of lignin and crosslinking agent, lignin particle moisture is being prepared
Amination modifying is carried out to lignin using Mannich method before dispersion liquid, is grafted to organic amine group on lignin molecule.Crosslinking agent
It can crosslink and react simultaneously with amido, the hydroxyl in aminated lignin molecule, crosslinking degree increases, and the lignin of formation is micro-
Capsule-wall is finer and close.
3, using the adjustable control of lignin capsule size prepared by the present invention.In aminated lignin particle dispersion system
The standby stage, the size of lignin particle can be changed by the concentration and speed that change drop acid；In emulsifying stage, by changing amination
The standby Pickering cream of the adjustable controls such as the concentration of lignin particle, the emulsion strength of oil-water ratio and homogenizer, emulsification times
The size of size droplet diameter, so as to regulate and control to prepare the size of microcapsules.
4, lignin has the characteristic of alkali-soluble acid analysis, i.e. lignin particles can dissolve under alkaline condition, in acid condition
Under can be precipitated, therefore microcapsules prepared by the present invention can change the stability of microcapsule wall material by changing pH value, thus
The rate of release of pesticide is controlled, i.e., microcapsules prepared by the present invention have pH responsiveness.In addition, most of pesticide is in acid condition
Lower stabilization, and it is degradable unstable under alkaline condition.System is slant acidity condition during preparation method of the present invention, is conducive to
Pesticide is stabilized.
5, the present invention is effectively dropped using the lignin from industrial by-products as the primary raw material of synthesis microcapsule wall material
The production cost of humble capsule realizes the resource utilization of abandoned biomass, reduces the cost of microcapsules；Simultaneously because wooden
Element is degradable, so that microcapsules can slowly degrade in nature, it is environmentally friendly.
6, since what is be crosslinked the present invention is based on O/W type Pickering emulsion interface prepares lignin wall material microcapsules,
Pesticide can be dissolved in composition oil in organic solvent in emulsion preparation process and mutually carry out subsequent operation again, so as to realize wood
Encapsulating of the quality microcapsules to pesticide.As hindered phenol structure a large amount of in the lignin molecule of wall material be conducive to improve it is photosensitive or
The stability of oxygen-sensitive pesticide.
Detailed description of the invention
Fig. 1 is the grain size distribution of lignin pesticide micro capsule prepared by embodiment 1.
Fig. 2 is the microscope figure of lignin pesticide micro capsule prepared by embodiment 1.
Fig. 3 is the SEM figure of lignin microcapsules prepared by embodiment 1.
Fig. 4 is the wall material infrared spectrum of lignin pesticide micro capsule prepared by embodiment 1.
Fig. 5 is the sustained release performance curve of AVM@ALMC and OP-AVM prepared by embodiment 1.
Fig. 6 is the anti-photolysis performance curve of AVM@ALMC and OP-AVM prepared by embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Material involved in the following example can be obtained from commercial channel.Dosage of each component is in terms of mass parts.
Embodiment 1:
(1) preparation of aminated lignin particle water dispersion liquid: in 10 mass parts bamboo pulp alkali lignins be added sodium hydroxide and
Water adjust concentration of polymer solution be 20%, pH 9, heating makes reaction system be warming up to 50 DEG C, and stirs and ensure that lignin is complete
Dissolution.10 mass parts ethylenediamines are then added, and system is made to be warming up to 70 DEG C.47 mass are slowly added into system with peristaltic pump
Part formalin (mass concentration 37%), following reaction 3h, rotary evaporation are dried to obtain aminated lignin.
(2) preparation of aminated lignin particle dispersion: the above-mentioned aminated lignin of 1 mass parts is taken to be added to 100 mass parts
In water, sodium hydrate regulator solution pH to 9, which is added, is completely dissolved lignin, and after filtering, nitric acid is added dropwise into filtrate extremely
PH value of solution is 4, is continuously stirred, and aminated lignin particle dispersion can be obtained.
(3) preparation of Pickering lotion: the aminated lignin particle dispersion and 0.1 mass parts of step (2) preparation
Glutaraldehyde and 0.3 mass parts dihydroxymethyl ethylene urea are uniformly mixed as water phase；0.1 mass parts avermectin and 10 mass parts
Oily phase is made in cyclohexanone mixed dissolution；Then it is mutually mixed with water phase oily, carries out emulsification treatment at 8000rpm using mulser
20min obtains lignin O/W Pickering lotion.
(4) it carries the synthesis of pesticide lignin microcapsules: 0.01 mass parts zinc nitrate being added in above-mentioned emulsion, in 50rpm
Mixing speed, react 1h at 80 DEG C after, obtain lignin microcapsules water slurry, filter, washing, it is dry after to obtain solid micro-
Capsule particle.
Embodiment 2:
(1) sodium hydroxide and water the preparation of aminated lignin particle water dispersion liquid: are added in 10 mass parts enzymolysis xylogens
Adjust concentration of polymer solution be 40%, pH 10, heating makes reaction system be warming up to 50 DEG C, and stirs and ensure that lignin particle is complete
Fully dissolved.20 mass parts ethylenediamines are then added, and system is made to be warming up to 90 DEG C.70 matter are slowly added into system with peristaltic pump
It measures part formalin (mass concentration 37%), following reaction 5h, rotary evaporation is dried to obtain aminated lignin.
(2) preparation of aminated lignin particle dispersion: the above-mentioned aminated lignin of 2 mass parts is taken to be added to 100 mass parts
In water, sodium hydrate regulator solution pH to 10, which is added, is completely dissolved lignin, and after filtering, nitric acid is added dropwise into filtrate extremely
PH value of solution is 6, is continuously stirred, and aminated lignin particle dispersion can be obtained.
(3) preparation of Pickering lotion: the aminated lignin particle dispersion and 1.2 mass parts of step (2) preparation
1,2,3,4- butane tetracarboxylic acid is uniformly mixed as water phase；1 mass parts cyhalothrin and 20 mass parts cyclohexanone mixed dissolutions
Oily phase is made；Then it is mutually mixed with water phase oily, carries out emulsification treatment 15min at 11000rpm using mulser, obtain wood
Quality O/W Pickering lotion.
(4) it carries the synthesis of pesticide lignin microcapsules: 0.02 mass parts sodium hypophosphite being added in above-mentioned emulsion,
The mixing speed of 100rpm after reacting 3h at 60 DEG C, obtains lignin microcapsules water slurry, filters, washing, it is dry after obtain
Solid microcapsule granule.
Embodiment 3:
(1) preparation of aminated lignin particle water dispersion liquid: sodium hydroxide and water is added in 10 mass parts Wheat Straw Lignin from Alkali Pulping
Adjust concentration of polymer solution be 25%, pH 11, heating makes reaction system be warming up to 50 DEG C, and stirs and ensure that lignin particle is complete
Fully dissolved.15 mass parts hexamethylene diamines are then added, and system is made to be warming up to 80 DEG C.55 matter are slowly added into system with peristaltic pump
It measures part formalin (mass concentration 37%), following reaction 4h, rotary evaporation is dried to obtain aminated lignin.
(2) preparation of aminated lignin particle dispersion: the above-mentioned aminated lignin of 4 mass parts is taken to be added to 100 mass parts
In water, sodium hydrate regulator solution pH to 10, which is added, is completely dissolved lignin, and after filtering, nitric acid is added dropwise into filtrate extremely
PH value of solution is 4, is continuously stirred, and aminated lignin particle dispersion can be obtained.
(3) preparation of Pickering lotion: the aminated lignin particle dispersion and 4 mass parts two of step (2) preparation
Methylol ethylene urea is uniformly mixed as water phase；2 mass parts avermectin and 30 mass parts isophorone mixed dissolutions are made
Oily phase；Then it is mutually mixed with water phase oily, carries out emulsification treatment 5min at 12000rpm using mulser, obtain lignin O/
W Pickering lotion.
(4) it carries the synthesis of pesticide lignin microcapsules: 0.04 mass parts zinc nitrate being added in above-mentioned emulsion, in 150rpm
Mixing speed, react 8h at 50 DEG C after, obtain lignin microcapsules water slurry, filter, washing, it is dry after to obtain solid micro-
Capsule particle.
Embodiment 4:
(1) preparation of aminated lignin particle water dispersion liquid: sodium hydroxide and water is added in 10 mass parts wood pulp alkali lignins
Adjust concentration of polymer solution be 35%, pH 11, heating makes reaction system be warming up to 50 DEG C, and stirs and ensure that lignin particle is complete
Fully dissolved.15 mass parts hexamethylene diamines are then added, and system is made to be warming up to 70 DEG C.95 matter are slowly added into system with peristaltic pump
It measures part formalin (mass concentration 37%), following reaction 4h, rotary evaporation is dried to obtain aminated lignin.
(2) preparation of aminated lignin particle dispersion: the above-mentioned aminated lignin of 6 mass parts is taken to be added to 100 mass parts
In water, sodium hydrate regulator solution pH to 11, which is added, is completely dissolved lignin, and after filtering, nitric acid is added dropwise into filtrate extremely
PH value of solution is 5, is continuously stirred, and aminated lignin particle dispersion can be obtained.
(3) preparation of Pickering lotion: aminated lignin particle dispersion, 1 mass parts penta step (2) preparation
Dialdehyde and 3 mass parts citric acids are uniformly mixed as water phase；8 mass parts chlopyrifos and 40 mass parts isophorone mixed dissolutions
Oily phase is made；Then it is mutually mixed with water phase oily, carries out emulsification treatment 10min at 12000rpm using mulser, obtain wood
Quality O/W Pickering lotion.
(4) it carries the synthesis of pesticide lignin microcapsules: 0.06 mass parts sodium hypophosphite being added in above-mentioned emulsion,
The mixing speed of 200rpm after reacting 2h at 75 DEG C, obtains lignin microcapsules water slurry, filters, washing, it is dry after obtain
Solid microcapsule granule.
Embodiment 5:
(1) preparation of aminated lignin particle water dispersion liquid: sodium hydroxide and water is added in 10 mass parts bagasse alkali-lignins
Adjust concentration of polymer solution be 30%, pH 12, heating makes reaction system be warming up to 50 DEG C, and stirs and ensure that lignin particle is complete
Fully dissolved.20 mass parts diethylenetriamines are then added, and system is made to be warming up to 80 DEG C.Slowly added into system with peristaltic pump
Enter 70 mass parts formalins (mass concentration 37%), following reaction 4h, rotary evaporation is dried to obtain aminated lignin.
(2) preparation of aminated lignin particle dispersion: the above-mentioned aminated lignin of 8 mass parts is taken to be added to 100 mass parts
In water, sodium hydrate regulator solution pH to 12, which is added, is completely dissolved lignin, and after filtering, nitric acid is added dropwise into filtrate extremely
PH value of solution is 5, is continuously stirred, and aminated lignin particle dispersion can be obtained.
(3) preparation of Pickering lotion: aminated lignin particle dispersion, 4 mass parts penta step (2) preparation
Dialdehyde and 4 mass parts ethylene glycol diglycidylethers are uniformly mixed as water phase；10 mass parts cyhalothrins and 50 mass parts
Oily phase is made in cyclohexanone mixed dissolution；Then it mutually mixes with water phase oily, is carried out at emulsification at 11000rpm using mulser
8min is managed, lignin O/W Pickering lotion is obtained.
(4) it carries the synthesis of pesticide lignin microcapsules: 0.08 mass parts sodium chloride being added in above-mentioned emulsion, in 250rpm
Mixing speed, react 3h at 65 DEG C after, obtain lignin microcapsules water slurry, filter, washing, it is dry after to obtain solid micro-
Capsule particle.
Embodiment 6:
(1) preparation of aminated lignin particle water dispersion liquid: sodium hydroxide and water is added in 10 mass parts cotton stalk alkali lignins
Adjust concentration of polymer solution be 20%, pH 12, heating makes reaction system be warming up to 50 DEG C, and stirs and ensure that lignin particle is complete
Fully dissolved.20 mass parts diethylenetriamines are then added, and system is made to be warming up to 90 DEG C.Slowly added into system with peristaltic pump
Enter 95 mass parts formalins (mass concentration 37%), following reaction 5h, rotary evaporation is dried to obtain aminated lignin.
(2) preparation of aminated lignin particle dispersion: the above-mentioned aminated lignin of 10 mass parts is taken to be added to 100 mass parts
In water, sodium hydrate regulator solution pH to 12, which is added, is completely dissolved lignin, and after filtering, nitric acid is added dropwise into filtrate extremely
PH value of solution is 4, is continuously stirred, and aminated lignin particle dispersion can be obtained.
(3) preparation of Pickering lotion: the aminated lignin particle dispersion and 10 mass parts of step (2) preparation
Ethylene glycol diglycidylether is uniformly mixed as water phase；12 mass parts chlopyrifos and 60 mass parts cyclohexanone mixed dissolution systems
At oily phase；Then it is mutually mixed with water phase oily, carries out emulsification treatment 10min at 13000rpm using mulser, obtain wooden
Plain O/W Pickering lotion.
(4) it carries the synthesis of pesticide lignin microcapsules: 0.1 mass parts sodium chloride being added in above-mentioned emulsion, in 300rpm
Mixing speed, react 4h at 75 DEG C after, obtain lignin microcapsules water slurry, filter, washing, it is dry after to obtain solid micro-
Capsule particle.
Embodiment effect explanation:
Illustrate effect by taking embodiment 1 as an example.
Fig. 1 is the grain of lignin pesticide micro capsule in 1 water slurry of embodiment using the measurement of Malvern laser particle analyzer
Diameter distribution, it is seen that there is bimodal distribution, wherein ebb is in 250nm or so, and peak is at 1.5 μm or so.Fig. 2 is the embodiment of the present invention
The optical microscope picture of the lignin pesticide micro capsule of 1 preparation, it can be seen that microcapsules are in regular spherical shape.Fig. 3 is this reality
Apply the scanning electron microscope (SEM) photograph of the lignin pesticide micro capsule of example preparation, it can be seen that microcapsules are in regular spherical shape, and surface is more smooth,
Average grain diameter is about 1 μm, consistent with laser particle analyzer measurement result.
Really reaction is crosslinked in order to further verify lignin and forms microcapsules, to the used raw material alkali of embodiment 1
Lignin (AL) and effect microcapsule wall (ALMC) carry out infrared spectrum characterization, as shown in Figure 4.For raw material alkali lignin, phenol
Absorption peak caused by stretching vibration on hydroxyl and alcoholic extract hydroxyl group is in 3405-3450cm-1Place；2933cm-1It is nearby methyl and methylene
C-H stretching vibration peak in base；1033-1030cm-1Neighbouring absorption peak belongs to C-O stretching vibration absworption peak.With raw material alkali
Lignin is compared, and cyst wall ALMC is in 2933cm-1And 1033cm-1The absorption peak of the two positions has obvious reinforcement.This is because alkali
After lignin and crosslinking agent reaction, caused by ehter bond and methene key increase in molecular structure.Therefore infrared spectrum confirms wood
Quality forms cyst wall by cross-linking reaction.
Determine the application performance for carrying pesticide lignin microcapsules.From fig. 5, it can be seen that raw medicine used in embodiment 1
Avermectin (OP-AVM) its Cumulative release amount after 48h is 93.83%, and rate of release is very fast.And micro- glue after being encapsulated
Capsule AVM@ALMC rate of release is moderate, and Cumulative release amount is 61.47% after 48h.It is compared with raw medicine OP-AVM, AVM@ALMC is one
Determine the rate of release that can slow down avermectin in degree.From fig. 6, it can be seen that with the extension raw medicine of ultraviolet lighting time
The content of OP-AVM declines rapidly, it is effectively retained rate and there was only 10.68% after illumination 72h.And the Avermectin in AVM@ALMC
Plain degradation rate is slower, its retention rate remains at higher level after illumination 72h, is 85.05%.This is because lignin has
There is the good ultraviolet performance of absorption, uses lignin as the wall material of microcapsules, have to Photosensitive pesticide avermectin good
Protective effect effectively improves its photostability.
The test method of all data is as follows in Fig. 5 and Fig. 6:
(1) HPLC measure avermectin content: analytical column be Agilent ZORBAX SB-C18 column (4.6 × 250mm,
5.0 μm), mobile phase is V (methanol): V (water)=88:12；Flow velocity is 1.0mL/min；Detector is UV detector, detects wave
Long 245nm, sample volume 20 μ L, 40 DEG C of column temperature, using standard curve standard measure.
(2) 72 hours burst sizes: accurately weighing a certain amount of microcapsules solid, to be dispersed in 20mL 80wt% alcohol-water mixed
It closes in solution, this dispersion liquid is transferred in the dialysis band of 10000D, bag filter is placed in 100mL 80wt% alcohol-water and is mixed
The avermectin content in sustained-release liquid is measured in solution, after 72 hours.
(3) 72 hours photodissociation amounts: accurately weighing a certain amount of microcapsules solid and be dispersed in 5mL water, old in ultraviolet test
Change case in by 72 hours ultraviolet light (ultraviolet lamp power 30W, wavelength 340nm, 42 DEG C of temperature) afterwards measure avermectin it is residual
Deposit content.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the load pesticide lignin microcapsules based on emulsion interface crosslinking, it is characterised in that first use Manny
Uncommon method prepares aminated lignin, then alkali-soluble acid analysis prepares aminated lignin particle dispersion in water, crosslinking agent is added, as water
Phase；Pesticide and organic solvent are mixed as oily phase；Water phase and oil are mixed, emulsified, O/W type Pickering lotion is prepared；
Catalyst is added, heat cross-linking reaction obtains carrying pesticide lignin microcapsules.
2. the preparation method of the load pesticide lignin microcapsules according to claim 1 based on emulsion interface crosslinking, special
Sign is that dosage of each component is, mass parts: 100 parts of water；1~10 part of aminated lignin；0.4~10 part of crosslinking agent；Pesticide 0.1~
12 parts；10~60 parts of organic solvent；0.01~0.1 part of catalyst.
3. the preparation method of the load pesticide lignin microcapsules according to claim 1 based on emulsion interface crosslinking, special
Sign is: the use Mannich method prepares aminated lignin and is prepared by including the following steps: lignin is dissolved in pH 9
In~12 lye, aminating agent, formalin is added, heating reaction obtains aminated lignin.
4. the preparation method of the load pesticide lignin microcapsules according to claim 3 based on emulsion interface crosslinking, special
Sign is: lignin used, aminating agent, formaldehyde mass ratio be 10:(10~20): (47~95)；Heating reaction for
3~5h is reacted at 70~90 DEG C.
5. the preparation method of the load pesticide lignin microcapsules according to claim 3 based on emulsion interface crosslinking, special
Sign is: the aminating agent includes at least one of ethylenediamine, hexamethylene diamine and diethylenetriamines；The lignin packet
Include at least one of alkali lignin and enzymolysis xylogen；The alkali lignin includes pulp black liquor, bamboo pulp black liquor, Straw Pulp
One of black liquor, reed pulp black liquor, bagasse black liquor, Dracaena straw pulp black liquor, cotton stalk pulp black liquor and cotton pulp black liquor, through peracid
Lignin by acid separation powder after analysis is dry；The enzymolysis xylogen includes that the cellulose fermentation in plant material is prepared alcohol
The lignin of separation and Extraction in residue.
6. the preparation method of the load pesticide lignin microcapsules according to claim 1 based on emulsion interface crosslinking, special
Sign is: the crosslinking agent: including glutaraldehyde, dihydroxymethyl ethylene urea, citric acid, 1,2,3,4- butane tetracarboxylic acid, second two
At least one of alcohol diglycidyl ether；The pesticide is fat-soluble pesticide；The organic solvent includes toluene, hexamethylene
One of ketone and isophorone；The catalyst includes at least one of sodium hypophosphite, zinc nitrate and sodium chloride.
7. the preparation method of the load pesticide lignin microcapsules according to claim 1 based on emulsion interface crosslinking, special
Sign is: the emulsification is in 5~20min of the emulsified processing of 8000~13000rpm；The described heat cross-linking reaction for
The mixing speed of 50~300rpm reacts 1~8h at 50~80 DEG C.
8. the preparation method of the load pesticide lignin microcapsules according to claim 1 based on emulsion interface crosslinking, special
Sign is in preparation method that alkali-soluble acid analysis prepares aminated lignin particle dispersion to aminated lignin in water, refers to amination wood
Quality is dissolved in lye, adds acid, and lignin is made to be precipitated to form aminated lignin particle dispersion.
9. the preparation method of the load pesticide lignin microcapsules according to claim 1 based on emulsion interface crosslinking, special
Sign be specifically includes the following steps:
(1) preparation of aminated lignin particle dispersion: being added to the water aminated lignin, and it is 9~12 that alkali, which is added, and adjusts pH,
Aminated lignin solution is obtained, filtrate is filtered to take, adding acid to pH is 4~6, obtains aminated lignin particle dispersion；
(2) prepared by Pickering lotion: crosslinking agent is added as water phase in aminated lignin particle dispersion, pesticide is dissolved in
As oily phase in organic solvent, after water-oil phase mixing, emulsification obtains the particle-stabilised oil-in-water type Pickering of lignin
Lotion；
(3) it carries the synthesis of pesticide lignin microcapsules: catalyst being added into lotion, heat cross-linking reaction obtains carrying pesticide wood
Quality microcapsule suspensions.
10. a kind of load pesticide lignin microcapsules based on emulsion interface crosslinking, it is characterised in that according to claim 1~9 times
Preparation method described in one obtains.
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| CN114349978A (en) * | 2022-02-15 | 2022-04-15 | 中国农业大学 | Phenolated lignin-based O/W type Pickering emulsion and preparation method and application thereof |
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| CN113508738A (en) * | 2021-05-31 | 2021-10-19 | 潍坊郭牌农业科技有限公司 | Nutrient soil for small potted watermelons and preparation method of nutrient soil |
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| CN115804373A (en) * | 2022-12-08 | 2023-03-17 | 上海师范大学 | Nano cellulose based ultraviolet-resistant pesticide microcapsule and preparation method thereof |
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