CN104012528B - A kind of preparation method containing organosilicon pesticide micro capsule - Google Patents
A kind of preparation method containing organosilicon pesticide micro capsule Download PDFInfo
- Publication number
- CN104012528B CN104012528B CN201410266027.5A CN201410266027A CN104012528B CN 104012528 B CN104012528 B CN 104012528B CN 201410266027 A CN201410266027 A CN 201410266027A CN 104012528 B CN104012528 B CN 104012528B
- Authority
- CN
- China
- Prior art keywords
- acid
- micro capsule
- gelatin
- preparation
- organosilicon
- 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.)
- Expired - Fee Related
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Containing a preparation method for organosilicon pesticide micro capsule, comprise (1) and gelatin and anionic organic silicon surfactant are dissolved in the water of 20-60 DEG C; (2) sodium carboxymethylcellulose is dissolved in the water of 70 ~ 90 DEG C; Join in the solution of step (1); (3) agricultural-chemical suspension liquid and gelatin, sodium carboxymethylcellulose and anionic organic silicon surfactant are joined in the solution of step (2), dispersed with stirring, obtain O/W type emulsion; (4) add acid and water, complex coacervation occurs; Cooling, adds crosslinking agent and makes it curing cross-linked, continues reaction; (5) aqueous slkali adjust ph is added, temperature reaction.The present invention plays the feature of organosilicon height chemically stable, low surface tension, improves pesticide micro capsule to the spreading ability of plant leaf surface, thus improves the availability of agricultural chemicals and extend the lasting period of agricultural chemicals; The pollution of environment in agricultural production process can be reduced, reduce agriculture production cost.
Description
Technical field
The present invention relates to a kind of preparation method containing organosilicon pesticide micro capsule, belong to pesticide micro capsule preparing technical field.
Background technology
At present, the main formulation of agricultural chemicals is missible oil, needs to consume a large amount of organic solvent, not only causes environmental pollution but also cause the wasting of resources.Efficient, low toxicity, free of contamination environmentally friendly agricultural chemicals appearance is called in the environmental protection of society and sustainable development.The features such as pesticide micro capsule has safety, low toxicity, efficient, low-residual, Environmental compatibility are good, the lasting period is long are novel form (US20110301036A1, the 2011.12.8 of modern environment friendly agricultural chemicals; US20130095158A1,2013.4.18).
Publication number CN102349509A discloses a kind of preparation method of lignin urea-formaldehyde pesticide microcapsule, the method with modified lignin resin, formaldehyde and urea for monomer, under base catalysis, form soluble prepolymer is continuous phase, with agricultural chemicals and organic solvent for disperse phase, at acid condition, situ aggregation method is adopted to obtain lignin urea aldehyde radical microcapsules.These microcapsules adopt paper-making industry discarded object Wheat Straw Lignin from Alkali Pulping to be cyst material, can reduce production cost, but the more difficult control of its reaction condition.Wang etc. with Avermectin active substance be capsule-core, carbamide resin for cyst material, adopt interfacial polymerization prepare avermectin microcapsule (LeileiWang, etal., AdvancedMaterialsResearch, 2013, Vol.634-638, p1090 ~ 1094).The Microcapsules Size wider distribution that this legal system is standby, and the reaction monomers toxicity adopted is comparatively large, there is potential safety hazard in production process to producers.Kong etc. for capsule-core, with gelatin and gum Arabic for cyst material, adopt complex coacervation to obtain microcapsules (XiangzhengKong with insect sex pheromone (lauryl alcohol), etal., BiomedMicrodevices, 2009, Vol.11, p275 ~ 285).Microcapsules Size prepared by this method is more even, sustained release performance is better, but due to gelatin and gum Arabic be all natural prodcuts, stability is relatively poor, and gum Arabic is a kind of imported product concerning China, large-scale use will become expensive raw material.Therefore find a kind of relative low price, and the polyanionic polymer of stable performance as an alternative product are the problems primarily solved.
Publication number CN102893985A discloses a kind of method being prepared avermectin microcapsule by complex coacervation, the method replaces gum Arabic with sodium alginate and gelatin is combined into cyst material, with Avermectin active substance for capsule-core, complex coacervation is adopted to prepare avermectin microcapsule.But the spreading property of these microcapsules needs to be improved further.How to improve the spreading property of microcapsules, thus improve agricultural chemicals availability, the lasting period extending agricultural chemicals is the emphasis that people study always.
Summary of the invention
The object of the invention is, overcome the deficiencies in the prior art, a kind of preparation method containing organosilyl pesticide micro capsule is provided.
Realizing technical scheme of the present invention is, the present invention introduces silicon-containing surfactant in cyst material, under suitable stir speed (S.S.), make agricultural-chemical suspension liquid be dispersed in aqueous phase under emulsification, by regulation system pH value, there is complex coacervation, prepare stable, that even particle size distribution, spreading property are good spherical microcapsule under suitable process conditions.
A kind of preparation method containing organosilyl pesticide micro capsule of the present invention, comprises the steps:
(1) be that the gelatin of 0.5 ~ 10:1 and anionic organic silicon surfactant are dissolved in the water of 20-60 DEG C by mass ratio;
(2) sodium carboxymethylcellulose is dissolved in the water of 70 ~ 90 DEG C; Join in step (1) described solution, the mass ratio of sodium carboxymethylcellulose and gelatin is 0.05 ~ 1:1;
(3) agricultural-chemical suspension liquid is joined in the solution described in step (2), dispersed with stirring 1 ~ 100 minute, obtain O/W type emulsion; Wherein the pesticide volume of agricultural-chemical suspension liquid and the mass ratio of gelatin, sodium carboxymethylcellulose and anionic organic silicon surfactant summation are 0.20 ~ 10:1;
(4) add acid and water, complex coacervation occurs; Cool to 0 ~ 15 DEG C, add crosslinking agent and make it curing cross-linked, continue reaction 2 ~ 20 hours;
(5) add aqueous slkali, adjust ph, to 7.0 ~ 12, is warming up to 30 ~ 60 DEG C of reactions 1 ~ 3 hour.
The general structure of described anionic organic silicon surfactant is:
M=0-500, n=4-60, R=CH in formula
2, CHCH
3, M is alkali metal.
The number-average molecular weight of the anionic organic silicon surfactant in the present invention is 778 ~ 48202.
Anionic organic silicon surfactant in the present invention is the polymer of same molecular weight distribution, or the mixture of the polymer of two or more different molecular weight distribution.
Acid in step of the present invention (3) is acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid or tartaric acid, and the mass percent concentration of acid is 0.05 ~ 20%; Described stir speed (S.S.) is 220 ~ 1000rpm.
Crosslinking agent in step of the present invention (4) is one or more in formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, butanedial, and the mass percent concentration of crosslinking agent is 5 ~ 40%.
The present invention adopt agricultural-chemical suspension liquid be following any one: permethrin, carbaryl, meta-tolyl-N-methylcarbamate (MTMC), phoxim, chlopyrifos.
The present invention's beneficial effect is compared with the prior art, the present invention is coordinated by sodium carboxymethylcellulose and anionic organic silicon surfactant, overcome gum Arabic easily degrade as natural polymer and affect the shortcoming of properties of microcapsules, play the high chemically stable of anionic organic silicon surfactant, the feature of low surface tension, improve pesticide micro capsule to the spreading ability of plant leaf surface, thus improve the availability of agricultural chemicals and extend the lasting period of agricultural chemicals.And prepare stable, the better spherical pesticide micro capsule of slow release by suitable composition of raw materials and technique.This preparation method is simple to operate, and cost is low, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is in embodiment 1, with gelatin, sodium carboxymethylcellulose and organosilicon carboxylic acid potassium surfactant for the optical microscope picture of pesticide micro capsule prepared by wall material;
Fig. 2 is in embodiment 1, with gelatin, sodium carboxymethylcellulose and organosilicon carboxylic acid potassium surfactant for the grain size distribution of pesticide micro capsule prepared by wall material; Abscissa is particle diameter, and ordinate is quantity.
Embodiment
By following embodiment, the present invention is described in further detail:
Embodiment 1
Gelatin being made into 40 gram mass specific concentrations is the aqueous solution of 10%, and number-average molecular weight is 8.0 grams, the organosilicon carboxylic acid potassium surfactant of 48202, is incubated for subsequent use at 45 DEG C.Sodium carboxymethylcellulose being made into 20 gram mass specific concentrations is the aqueous solution of 1.0%, is incubated for subsequent use at 80 DEG C;
Auxiliary agent being joined 12.2 gram mass specific concentrations is in 20% permethrin milk oil, at 45 DEG C, sonic oscillation makes it to become homodisperse agricultural-chemical suspension liquid, join in above-mentioned gelatin/sodium carboxymethylcellulose/organosilicon carboxylic acid aqueous solutions of potassium, 30 minutes are disperseed with the stir speed (S.S.) of 500rpm, obtained O/W type emulsion, at 45 DEG C, with 20% aqueous acetic acid, the pH value of system is down to 4.5, in stirring, temperature is slowly down to 15 DEG C, the glutaraldehyde water solution of 5 milliliter 25% is added drop-wise in above-mentioned system, make microcapsule wall curing cross-linked, continue reaction 10 hours, add the pH value to 7.0 of 3% sodium hydroxide solution regulation system, reaction is continued 1 hour at 60 DEG C, obtain containing organosilicon pesticide micro capsule.
Embodiment 2
Gelatin being made into 32 gram mass specific concentrations is the aqueous solution of 10%, and number-average molecular weight is the organosilicon carboxyl acid natrium surfactant 3.2 grams of 778, is incubated for subsequent use at 60 DEG C.Sodium carboxymethylcellulose being made into 320 gram mass specific concentrations is the aqueous solution of 1.0%, is incubated for subsequent use at 70 DEG C;
Auxiliary agent and 1.92 grams of former medicines of carbaryl are joined in tetrachloro-ethylene, at 45 DEG C, sonic oscillation makes it to become the homodisperse agricultural-chemical suspension liquid that quality than concentration is 10%, join in above-mentioned gelatin/sodium carboxymethylcellulose/organosilicon carboxylic acid sodium aqueous solution, 100 minutes are disperseed with the stir speed (S.S.) of 350rpm, obtained O/W type emulsion, at 45 DEG C, with 10% aqueous citric acid solution, the pH value of system is down to 4.5, in stirring, temperature is slowly down to 0 DEG C, the glyoxal water solution of 3 milliliter 40% is added drop-wise in above-mentioned system, make microcapsule wall curing cross-linked, continue reaction 20 hours, add the pH value to 9.0 of 3% sodium hydroxide solution regulation system, reaction is continued 2 hours at 30 DEG C, obtain containing organosilicon pesticide micro capsule.
Embodiment 3
Gelatin being made into 50 gram mass specific concentrations is the aqueous solution of 10%, and number-average molecular weight is the organosilicon carboxyl acid natrium surfactant 1.0 grams of 47242, is incubated for subsequent use at 45 DEG C.Sodium carboxymethylcellulose being made into 100 gram mass specific concentrations is the aqueous solution of 1.0%, is incubated for subsequent use at 90 DEG C;
Auxiliary agent and 70 grams of former medicines of meta-tolyl-N-methylcarbamate (MTMC) are joined in tetrachloro-ethylene, at 45 DEG C, sonic oscillation makes it to become homodisperse agricultural-chemical suspension liquid, join in above-mentioned gelatin/sodium carboxymethylcellulose/organosilicon carboxylic acid sodium aqueous solution, 1 minute is disperseed with the stir speed (S.S.) of 1000rpm, obtained O/W type emulsion, at 45 DEG C, with 0.05% aqueous sulfuric acid, the pH value of system is down to 4.5, in stirring, temperature is slowly down to 0 DEG C, the formalin of 3 milliliter 37% is added drop-wise in above-mentioned system, make microcapsule wall curing cross-linked, continue reaction 10 hours, add the pH value to 9.0 of 3% sodium hydroxide solution regulation system, reaction is continued 3 hours at 45 DEG C, obtain containing organosilicon pesticide micro capsule.
Embodiment 4
Gelatin being made into 100 gram mass specific concentrations is the aqueous solution of 10%, and number-average molecular weight is 1.0 grams, the organosilicon carboxylic acid potassium surfactant of 46362, is incubated for subsequent use at 20 DEG C.Sodium carboxymethylcellulose being made into 50 gram mass specific concentrations is the aqueous solution of 1.0%, is incubated for subsequent use at 80 DEG C;
Auxiliary agent being joined 32 gram mass specific concentrations is in 25% chlorpyrifos ec, at 45 DEG C, sonic oscillation makes it to become homodisperse agricultural-chemical suspension liquid, join in above-mentioned gelatin/sodium carboxymethylcellulose/organosilicon carboxylic acid aqueous solutions of potassium, 30 minutes are disperseed with the stir speed (S.S.) of 500rpm, obtained O/W type emulsion, at 45 DEG C, with 1.0% aqueous hydrochloric acid solution, the pH value of system is down to 4.5, in stirring, temperature is slowly down to 5 DEG C, the butanedial aqueous solution of 10 milliliter 5% is added drop-wise in above-mentioned system, make microcapsule wall curing cross-linked, continue reaction 5 hours, add the pH value to 7.0 of 3% sodium hydroxide solution regulation system, reaction is continued 1 hour at 30 DEG C, obtain containing organosilicon pesticide micro capsule.
Embodiment 5
Gelatin being made into 40 gram mass specific concentrations is the aqueous solution of 10%, and number-average molecular weight is respectively the organosilicon carboxyl acid natrium surfactant 8.0 grams of 22662 and 15962, is incubated for subsequent use at 45 DEG C.Sodium carboxymethylcellulose being made into 20 gram mass specific concentrations is the aqueous solution of 1.0%, is incubated for subsequent use at 70 DEG C;
Auxiliary agent and 12.2 grams of phoxim crudes are joined in tetrachloro-ethylene, at 45 DEG C, sonic oscillation makes it to become homodisperse agricultural-chemical suspension liquid, join in above-mentioned gelatin/sodium carboxymethylcellulose/organosilicon carboxylic acid sodium aqueous solution, 100 minutes are disperseed with the stir speed (S.S.) of 220rpm, obtained O/W type emulsion, at 45 DEG C, with 5% phosphate aqueous solution, the pH value of system is down to 4.5, in stirring, temperature is slowly down to 0 DEG C, the acetaldehyde solution of 3 milliliter 37% is added drop-wise in above-mentioned system, make microcapsule wall curing cross-linked, continue reaction 10 hours, add the pH value to 12.0 of 3% sodium hydroxide solution regulation system, reaction is continued 3 hours at 60 DEG C, obtain containing organosilicon pesticide micro capsule.
Embodiment 6
Gelatin being made into 50 gram mass specific concentrations is the aqueous solution of 10%, and number-average molecular weight is respectively 1.0 grams, the organosilicon carboxylic acid potassium surfactant of 25162 and 26002, is incubated for subsequent use at 60 DEG C.Sodium carboxymethylcellulose being made into 40 gram mass specific concentrations is the aqueous solution of 5%, is incubated for subsequent use at 90 DEG C;
Auxiliary agent being joined 45 gram mass specific concentrations is in 20% permethrin milk oil, at 45 DEG C, sonic oscillation makes it to become homodisperse agricultural-chemical suspension liquid, join in above-mentioned gelatin/sodium carboxymethylcellulose/organosilicon carboxylic acid aqueous solutions of potassium, 60 minutes are disperseed with the stir speed (S.S.) of 350rpm, obtained O/W type emulsion, at 45 DEG C, with 10% aqueous citric acid solution, the pH value of system is down to 4.5, in stirring, temperature is slowly down to 15 DEG C, the formalin of the glutaraldehyde of 1.5 milliliter 25% and 1.0 milliliter 37% is added drop-wise in above-mentioned system, make microcapsule wall curing cross-linked, continue reaction 2 hours, add the pH value to 9.0 of 3% sodium hydroxide solution regulation system, reaction is continued 2 hours at 45 DEG C, obtain containing organosilicon pesticide micro capsule.
Embodiment 7
Gelatin being made into 32 gram mass specific concentrations is the aqueous solution of 10%, and number-average molecular weight is respectively 6.4 grams, the organosilicon carboxylic acid potassium surfactant of 45662 and 25162, is incubated for subsequent use at 20 DEG C.Sodium carboxymethylcellulose being made into 40 gram mass specific concentrations is the aqueous solution of 8%, is incubated for subsequent use at 80 DEG C;
Auxiliary agent and 25.6 grams of former medicines of carbaryl are joined in tetrachloro-ethylene, at 45 DEG C, sonic oscillation makes it to become homodisperse agricultural-chemical suspension liquid, join in above-mentioned gelatin/sodium carboxymethylcellulose/organosilicon carboxylic acid aqueous solutions of potassium, 1 minute is disperseed with the stir speed (S.S.) of 1000rpm, obtained O/W type emulsion, at 45 DEG C, by 5% aqueous tartaric acid solution, the pH value of system is down to 4.5, in stirring, temperature is slowly down to 10 DEG C, the acetaldehyde solution of the formaldehyde of 1.5 milliliter 37% and 1.5 milliliter 37% is added drop-wise in above-mentioned system, make microcapsule wall curing cross-linked, continue reaction 20 hours, add the pH value to 7.0 of 3% sodium hydroxide solution regulation system, reaction is continued 1 hour at 60 DEG C, obtain containing organosilicon pesticide micro capsule.
Embodiment 8
Gelatin being made into 50 gram mass specific concentrations is the aqueous solution of 10%, and number-average molecular weight is respectively the organosilicon carboxyl acid natrium surfactant 5.0 grams of 43882 and 32442, is incubated for subsequent use at 45 DEG C.Sodium carboxymethylcellulose being made into 50 gram mass specific concentrations is the aqueous solution of 1.0%, is incubated for subsequent use at 80 DEG C;
Auxiliary agent and 10.5 grams of phoxim crudes are joined in tetrachloro-ethylene, at 45 DEG C, sonic oscillation makes it to become homodisperse agricultural-chemical suspension liquid, join in above-mentioned gelatin/sodium carboxymethylcellulose/organosilicon carboxylic acid sodium aqueous solution, 30 minutes are disperseed with the stir speed (S.S.) of 500rpm, obtained O/W type emulsion, at 45 DEG C, with 20% aqueous acetic acid, the pH value of system is down to 4.5, in stirring, temperature is slowly down to 5 DEG C, the acetaldehyde solution of the glyoxal of 1.0 milliliter 40% and 1.0 milliliter 37% is added drop-wise in above-mentioned system, make microcapsule wall curing cross-linked, continue reaction 10 hours, add the pH value to 7.0 of 3% sodium hydroxide solution regulation system, reaction is continued 1 hour at 60 DEG C, obtain containing organosilicon pesticide micro capsule.
Claims (5)
1., containing a preparation method for organosilicon pesticide micro capsule, it is characterized in that, said method comprising the steps of:
(1) be that the gelatin of 0.5 ~ 10:1 and anionic organic silicon surfactant are dissolved in the water of 20-60 DEG C by mass ratio;
(2) sodium carboxymethylcellulose is dissolved in the water of 70 ~ 90 DEG C; Join in step (1) described solution, the mass ratio of sodium carboxymethylcellulose and gelatin is 0.05 ~ 1:1;
(3) agricultural-chemical suspension liquid is joined in the solution described in step (2), dispersed with stirring 1 ~ 100 minute, obtain O/W type emulsion; Wherein the pesticide volume of agricultural-chemical suspension liquid and the mass ratio of gelatin, sodium carboxymethylcellulose and anionic organic silicon surfactant summation are 0.20 ~ 10:1;
(4) add acid and water, complex coacervation occurs; Cool to 0 ~ 15 DEG C, add crosslinking agent and make it curing cross-linked, continue reaction 2 ~ 20 hours;
(5) add aqueous slkali, adjust ph, to 7.0 ~ 12, is warming up to 30 ~ 60 DEG C of reactions 1 ~ 3 hour;
The number-average molecular weight of described anionic organic silicon surfactant is 778 ~ 48202;
The general structure of described anionic organic silicon surfactant is:
M=0-500, n=4-60, R=CH in formula
2, CHCH
3, M is alkali metal.
2. a kind of preparation method containing organosilicon pesticide micro capsule according to claim 1, it is characterized in that, described anionic organic silicon surfactant is the polymer of same molecular weight distribution, or the mixture of the polymer of two or more different molecular weight distribution.
3. a kind of preparation method containing organosilicon pesticide micro capsule according to claim 1, it is characterized in that, described acid is acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid or tartaric acid, and the mass percent concentration of acid is 0.05 ~ 20%.
4. a kind of preparation method containing organosilicon pesticide micro capsule according to claim 1, is characterized in that, described crosslinking agent is one or more in formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, butanedial, and the mass percent concentration of crosslinking agent is 5 ~ 40%.
5. a kind of preparation method containing organosilicon pesticide micro capsule according to claim 1, it is characterized in that, described stir speed (S.S.) is 220 ~ 1000rpm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410266027.5A CN104012528B (en) | 2014-06-16 | 2014-06-16 | A kind of preparation method containing organosilicon pesticide micro capsule |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410266027.5A CN104012528B (en) | 2014-06-16 | 2014-06-16 | A kind of preparation method containing organosilicon pesticide micro capsule |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104012528A CN104012528A (en) | 2014-09-03 |
CN104012528B true CN104012528B (en) | 2016-04-13 |
Family
ID=51429759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410266027.5A Expired - Fee Related CN104012528B (en) | 2014-06-16 | 2014-06-16 | A kind of preparation method containing organosilicon pesticide micro capsule |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104012528B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110679591B (en) * | 2019-10-28 | 2021-09-21 | 上海悦联生物科技有限公司 | Pesticide composition and preparation method thereof |
CN112825854B (en) * | 2021-01-08 | 2022-05-17 | 杭州师范大学钱江学院 | Novel high-adhesion environment-friendly pesticide auxiliary agent and application and preparation method thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100372461C (en) * | 2005-07-20 | 2008-03-05 | 吴学民 | Method for producing pesticide micro capsule |
CN101609239B (en) * | 2009-06-11 | 2011-06-15 | 浙江大学 | Method for preparing electronic ink microcapsule containing organic silicon |
EA201290500A1 (en) * | 2009-12-15 | 2013-01-30 | Фмк Корпорейшн | MICROCAPSULES OF SILICON DIOXIDE WITH SLOW-DROPPED |
RU2567168C2 (en) * | 2010-06-07 | 2015-11-10 | ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи | Microcapsule suspensions including high levels of agriculturally active ingredients |
-
2014
- 2014-06-16 CN CN201410266027.5A patent/CN104012528B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN104012528A (en) | 2014-09-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103752236A (en) | Preparation method of double-layer wrapped essence micro-capsule | |
CN103242555B (en) | Acetylation lignin amphiphilic polymer nanometer colloid sphere and preparation method thereof | |
CN109362723B (en) | Pesticide-loaded lignin microcapsule based on emulsion interface crosslinking and preparation method thereof | |
CN101857730B (en) | Method for preparing microcapsule taking hydrophobic substance as core material by complex coacervation method | |
Fan et al. | Effect of emulsifier on poly (urea–formaldehyde) microencapsulation of tetrachloroethylene | |
CN101240224B (en) | Method for preparing sweet orange essence microcapsule | |
CN108940148B (en) | Preparation method of temperature-controlled slow-release essence microcapsule | |
CN108854878B (en) | Capric acid microcapsule and preparation method thereof | |
CN102349509B (en) | Method for preparing lignin urea-formaldehyde pesticide microcapsule | |
CN101461358A (en) | Oil-soluble pesticide nano capsules and preparation method thereof | |
CN104012528B (en) | A kind of preparation method containing organosilicon pesticide micro capsule | |
CN107384326A (en) | Gelatin chitosan nano silicon multinuclear microcapsules of storing energy through phase change preparation method | |
CN101779626A (en) | Uniconazole slow-release microcapsules and preparation method thereof | |
CN105076145A (en) | Microcapsule suspending agent containing azoxystrobin and preparation method thereof | |
CN102893985B (en) | Method for preparing abamectin microcapsules by complex coacervation | |
CN104437284A (en) | Preparation method of phase change microcapsule | |
CN107141818A (en) | A kind of chitin modified wet gel of sustained-release micro-spheres doping and preparation method thereof | |
CN103301791A (en) | Quercetin microcapsule and preparation method thereof | |
CN108355591A (en) | Dimethyl silicone polymer causes ethyl cellulose phase separation and prepares microcapsule method | |
CN109621851A (en) | A kind of preparation method of gamma-valerolactone/glycerol system high yield pulp1 lignin micro-nano ball | |
CN111838149B (en) | Nano-silicon dioxide coated quaternary ammonium salt chitosan composite antibacterial agent and preparation method thereof | |
CN103691373B (en) | A kind of method preparing Nano capsule | |
CN101844061B (en) | Method for preparing microcapsules using starch sodium octenyl succinate(SSOS) as wall material | |
CN111620956A (en) | Preparation method of starch caprylate and application of starch caprylate in pesticide microcapsule | |
CN103518712B (en) | Sustained-release chloroacetamide herbicide water dispersible granule and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160413 Termination date: 20200616 |
|
CF01 | Termination of patent right due to non-payment of annual fee |