CN112674093A - Environment-friendly copper abietate emulsion in water and preparation method thereof - Google Patents
Environment-friendly copper abietate emulsion in water and preparation method thereof Download PDFInfo
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- CN112674093A CN112674093A CN202110029932.9A CN202110029932A CN112674093A CN 112674093 A CN112674093 A CN 112674093A CN 202110029932 A CN202110029932 A CN 202110029932A CN 112674093 A CN112674093 A CN 112674093A
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Abstract
The invention discloses an environment-friendly copper abietate emulsion in water and a preparation method thereof. The preparation method comprises the following steps: preparing a rosin solution by adopting an environment-friendly solvent; adding inorganic copper salt into the rosin solution, and reacting under a reflux state; distilling to remove water in the system after the reaction is finished to obtain a copper abietate mother solution; adding an emulsifier into the copper abietate mother liquor to obtain an oil phase, and mixing an antifreezing agent and water to obtain a water phase; adding the oil phase into the water phase, and uniformly shearing to obtain the product. The preparation method of the environment-friendly copper abietate mother liquor does not use any organic solvent, has short reaction steps and can be used for conveniently preparing the copper abietate emulsion in water. Compared with the traditional synthesis of the copper abietate raw pesticide, the method disclosed by the invention has the advantages that the production cost is reduced, the production efficiency is improved, and meanwhile, the influence of an organic solvent on the environment is avoided. In addition, the copper abietate prepared by the method has good stability and high safety, and can be conveniently processed into various formulations such as aqueous emulsion, missible oil, granules and the like.
Description
Technical Field
The invention relates to an environment-friendly copper abietate emulsion in water and a preparation method thereof, belonging to the technical field of preparation of pesticide raw medicines and preparations.
Background
Among plant diseases, the kinds of diseases caused by fungal infection are the largest, and diseases caused by bacterial pathogens are the second. Bacterial diseases are diseases caused by infection with bacterial pathogens, such as soft rot, ulcer, bacterial wilt, spot disease and the like. After the plants are infected with bacterial diseases, the normal growth and development of the plants are influenced, and the great yield loss is caused. Chemical agents are important means for preventing and treating bacterial diseases, and some agents have good preventing and treating effects on bacterial diseases. However, the chemical agents for preventing and treating bacterial diseases have fewer varieties and smaller choice, and people commonly use antibiotic bactericides, inorganic copper bactericides, organic copper bactericides and the like to prevent and treat bacterial diseases in agricultural production. The organic copper bactericide has high copper ion content, high safety and high mixing performance, is a medicament for preventing and treating bacterial diseases with high cost performance, and has no resistance and good prospect. The copper abietate is one of organic copper bactericides, is a novel copper bactericide pesticide with high efficiency, low toxicity and broad spectrum, and has the new characteristics of long lasting period and convenient use.
The copper abietate has dual functions of prevention, protection and treatment as a bactericide. Can be used for preventing and treating common plant diseases caused by various fungi and bacteria, has obvious growth stimulation effect on vegetables, can be alternated with other bactericides, and has good spraying effect. The composition is used for preventing and treating various vegetable diseases such as downy mildew, epidemic disease, scab, anthracnose, bacterial angular leaf spot, eggplant damping off, tomato late blight and the like. The copper abietate can be mixed with various insecticides, pesticide bactericides and regulators for use at present, and can realize mutual synergism. Most importantly, the continuous use of the medicine can not generate drug resistance.
At present, the preparation method of the copper abietate emulsion in water is a traditional pesticide preparation process, namely, solid copper abietate raw material is taken as raw material, organic solvent is added after the raw material is crushed, the solid copper abietate raw material is heated to dissolve, and auxiliary agents such as wetting agent, emulsifier, antifreezing agent and the like and water are added to prepare the copper abietate emulsion in water. On one hand, harmful organic solvents such as toluene, xylene, ethyl acetate, alcohols and the like are needed in the synthesis process of the solid copper rosinate, or inorganic salts generated in the reaction process need to be washed away by water after the reaction is finished, so that a large amount of wastewater is generated, and the environmental protection property of the synthesis process of the solid copper rosinate is poor; on the other hand, in the process of processing the solid copper rosinate into the aqueous emulsion, organic solvents with good solubility such as toluene, xylene, cyclohexanone, alcohol and the like are also needed to be used for dissolving the copper rosinate, the dissolving process is slow, and the preparation efficiency and the environmental protection are poor. Therefore, a preparation method of the green and environment-friendly copper abietate aqueous emulsion is needed.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly copper abietate emulsion in water, which adopts an environment-friendly solvent to directly prepare copper abietate mother liquor, omits the process of dissolving solid raw medicines by using common aromatic hydrocarbon organic solvents such as benzene, toluene, xylene and the like, and then directly adds part of a surfactant, an antifreezing agent and water to prepare the copper abietate emulsion in water.
The preparation method of the copper abietate aqueous emulsion provided by the invention comprises the following steps:
s1, preparing a rosin solution by adopting an environment-friendly solvent;
s2, adding an inorganic copper salt into the rosin solution, and reacting under a reflux state; distilling to remove water in the system after the reaction is finished to obtain a copper abietate mother solution;
s3, adding an emulsifier into the copper abietate mother liquor to obtain an oil phase, and mixing an antifreezing agent and water to obtain a water phase; and adding the oil phase into the water phase, and uniformly shearing to obtain the copper abietate emulsion in water.
In the above preparation method, in step S1, the environmentally friendly solvent is at least one of soybean oil, corn oil, castor oil, palm oil, methylated vegetable oil, methyl oleate, rosin-based vegetable oil, and epoxidized soybean oil.
In the preparation method, in step S1, rosin and the environment-friendly solvent are mixed and heated to 90 to 110 ℃ until the rosin is completely dissolved to obtain the rosin solution;
the rosin can be at least one of gum rosin, wood rosin and dehydroabietic acid;
the mass ratio of the environment-friendly solvent to the rosin can be 0.5-6: 1, preferably 1 to 1.4: 1. 1: 1. 1.2: 1 or 1.4: 1.
in the above preparation method, in step S2, the inorganic copper salt may be at least one of basic copper carbonate, copper hydroxide and copper acetate.
In the preparation method, in the step S2, the reaction temperature may be 120 to 150 ℃, preferably 130 to 140 ℃, and the reaction time may be 1 to 3 hours, preferably 2 hours;
the mass ratio of the inorganic copper salt to the rosin can be 0.1-0.5: 1, preferably 0.1 to 0.4: 1. 0.18 to 0.34: 1. 0.18: 1 or 0.34: 1.
in the above preparation method, in step S2, when the inorganic copper salt is basic copper carbonate or copper hydroxide, the method further includes a step of adding acetic acid;
the mass ratio of the inorganic copper salt to the acetic acid may be 0.5-2: 1, preferably 0.7 to 1.5: 1. 0.7: 1 or 1.5: 1.
in the preparation method, in step S2, distillation is carried out at 100-140 ℃; the mass percentage of the copper rosinate in the copper rosinate mother liquor is 15-65%, preferably 40-50%.
In the above preparation method, in step S3, the oil phase is slowly added to the water phase with stirring.
In the above preparation method, in step S3, the emulsifier may be at least one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, phenethyl phenol polyoxyethylene polyoxypropylene block polyether, polyoxyethylene ether sulfate, fatty alcohol ether phosphate, aryl phenol ether phosphate, and alkyl polyether phosphate potassium salt;
the antifreeze agent can be at least one of ethylene glycol, propylene glycol and glycerol.
In the preparation method, in step S3, the copper abietate emulsion in water comprises the following components in percentage by mass:
20-60% of copper abietate mother liquor, 3-10% of emulsifier, 3-5% of antifreezing agent and the balance of water;
the method specifically comprises the following steps:
50-60% of copper abietate mother liquor, 6-10% of emulsifier, 4% of antifreezing agent and the balance of water;
50% of copper abietate mother liquor, 6% of emulsifier, 4% of antifreezing agent and the balance of water;
60% of copper abietate mother liquor, 8% of emulsifier, 4% of antifreezing agent and the balance of water.
The content of the copper rosinate in the environment-friendly copper rosinate aqueous emulsion prepared by the method is 3-40%, preferably 10-30%, 20%, 25% or 30%.
The preparation method of the environment-friendly copper abietate mother liquor provided by the invention does not use any organic solvent, has short reaction steps and can be used for conveniently preparing the copper abietate emulsion in water. Compared with the traditional synthesis of the copper abietate raw pesticide, the method disclosed by the invention has the advantages that the production cost is reduced, the production efficiency is improved, and meanwhile, the influence of an organic solvent on the environment is avoided. In addition, the copper abietate prepared by the method has good stability and high safety, and can be conveniently processed into various formulations such as aqueous emulsion, missible oil, granules and the like. Particularly, the copper abietate water emulsion prepared by the method has the advantages of good stability, convenient production, convenient use and low production cost.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of a 20% aqueous emulsion of copper rosinate
(1) Preparation of a rosin solution: 100 g of rosin is weighed, 140 g of methyl oleate is added, the mixture is heated to 100 ℃ until the rosin is completely dissolved, and the mixture is uniformly stirred to obtain a rosin solution.
(2) And (3) complexing reaction: and adding 34 g of copper acetate into the heated rosin solution, heating to 130 ℃, and stirring for reaction for 120min to obtain a dark blue solution.
(3) Preparing a copper abietate mother solution: after the reaction is finished, the temperature is kept at 130 ℃ for distillation, and water and acetic acid in the reaction are distilled out to obtain the blue-green 40% copper abietate mother liquor.
(4) Preparing the copper abietate water emulsion: preparing a copper rosinate oil phase: weighing 50 g of the copper rosinate mother liquor prepared in the step (3), adding 4 g of castor oil polyoxyethylene ether and 2 g of phenethyl phenol polyoxyethylene polyoxypropylene block polyether, and uniformly stirring to obtain a copper rosinate oil phase; 4 g of ethylene glycol and 40 g of deionized water were weighed and stirred uniformly to obtain an aqueous phase. Slowly adding the oil phase into the water phase in the stirring process, and uniformly shearing by using a high-speed shearing machine after the oil phase is added to obtain 100 g of 20% copper rosinate aqueous emulsion.
Example 2 preparation of a 25% aqueous emulsion of copper rosinate
(1) Preparation of a rosin solution: weighing 100 g of rosin, adding 120 g of methylated vegetable oil, heating to 110 ℃ until the rosin is completely dissolved, and uniformly stirring to obtain a rosin solution.
(2) And (3) complexing reaction: 18 g of basic copper carbonate and 26 g of acetic acid are added into the heated rosin solution, the temperature is raised to 135 ℃, and the mixture is stirred and reacted for 120min to obtain a dark blue solution.
(3) Preparing a copper abietate mother solution: after the reaction is finished, the temperature is kept at 135 ℃ for distillation, and water and acetic acid in the reaction are distilled out to obtain the turpentine acid copper mother liquor with the blue-green content of 50 percent.
(4) Preparing the copper abietate water emulsion: preparing a copper rosinate oil phase: weighing 50 g of the copper rosinate mother liquor prepared in the step (3), adding 3 g of polyoxyethylene ether sulfate and 3 g of phenethyl phenol polyoxyethylene polyoxypropylene block polyether, and uniformly stirring to obtain a copper rosinate oil phase; 4 g of ethylene glycol and 40 g of deionized water were weighed and stirred uniformly to obtain a water phase. Slowly adding the oil phase into the water phase during stirring, and uniformly shearing by using a high-speed shearing machine to obtain the copper rosinate water emulsion.
Example 3 preparation of a 30% aqueous emulsion of copper rosinate
(1) Preparation of a rosin solution: weighing 100 g of rosin, adding 100 g of rosin-based vegetable oil, heating until the rosin is completely dissolved, and uniformly stirring to obtain a rosin solution.
(2) And (3) complexing reaction: 34 g of copper hydroxide and 23 g of acetic acid are added into the heated rosin solution, the temperature is raised to 140 ℃, and the mixture is stirred and reacted for 120min to obtain a dark blue solution.
(3) Preparing a copper abietate mother solution: after the reaction is finished, the temperature is kept at 130 ℃ for distillation, water and acetic acid in the reaction are distilled out, and the blue-green copper abietate mother liquor with the content of 50 percent can be obtained.
(4) Preparing the copper abietate water emulsion: preparing a copper rosinate oil phase: weighing 60 g of the copper rosinate mother liquor prepared in the step (3), adding 5 g of castor oil polyoxyethylene ether and 3 g of phenethyl phenol polyoxyethylene polyoxypropylene block polyether, and uniformly stirring to obtain a copper rosinate oil phase; 4 g of ethylene glycol and 28 g of deionized water were weighed and stirred well to obtain an aqueous phase. Slowly adding the oil phase into the water phase in the stirring process, and uniformly shearing by using a high-speed shearing machine after adding to obtain 100 g of the copper rosinate aqueous emulsion.
The emulsion stability and the heat storage stability of the copper abietate aqueous emulsion prepared in examples 1-3 were tested, and the results are shown in Table 1, wherein the emulsion stability of the pesticide was measured according to GB/T1603-2001, the heat storage stability of the pesticide was measured according to GB/T19136-2003, and the particle size was measured by a Dandongbert BT-9300ST laser particle size distribution instrument.
As can be seen from the data in Table 1, the emulsion of the aqueous emulsion prepared by the method of the invention has qualified stability, small particle size and good heat storage stability.
TABLE 1 stability and particle size of copper rosinate aqueous emulsion
The existing method for preparing the copper abietate emulsion in water comprises the following steps: taking solid copper abietate as a raw material, crushing, adding 15-25% of organic solvent, heating to dissolve the solid copper abietate for about 40-60 min, and adding auxiliary agents such as wetting agent, emulsifier, antifreezing agent and water. Compared with the method, the method directly adopts environment-friendly dissolution to prepare the rosin mother liquor, so that an organic solvent is not adopted, and the time of the solvent is not needed.
The emulsion stability of the copper abietate water emulsion prepared by the two methods is qualified.
The particle size of the aqueous emulsion prepared by the existing method is 3-5 μm, while the particle size of the aqueous emulsion prepared by the method is about 0.5-2 μm, so the smaller the particle size of the preparation is, the higher the stability with time is, and the better the drug effect is.
Because the existing method adopts solid copper rosinate raw material, needs to use a solvent and also needs to stir, the cost of the auxiliary agent and the processing is high.
The comparison of the performance of the 20% copper abietate aqueous emulsion prepared by the method of the invention and the existing method is shown in the table 2.
TABLE 2 comparison of different aqueous emulsions of copper rosinate
Claims (10)
1. A preparation method of a copper abietate emulsion in water comprises the following steps:
s1, preparing a rosin solution by adopting an environment-friendly solvent;
s2, adding an inorganic copper salt into the rosin solution, and reacting under a reflux state; distilling to remove water in the system after the reaction is finished to obtain a copper abietate mother solution;
s3, adding an emulsifier into the copper abietate mother liquor to obtain an oil phase, and mixing an antifreezing agent and water to obtain a water phase; and adding the oil phase into the water phase, and uniformly shearing to obtain the copper abietate emulsion in water.
2. The method of claim 1, wherein: in step S1, the environmentally friendly solvent is at least one of soybean oil, corn oil, castor oil, palm oil, methylated vegetable oil, methyl oleate, rosin-based vegetable oil, and epoxidized soybean oil.
3. The production method according to claim 1 or 2, characterized in that: in the step S1, mixing rosin and the environment-friendly solvent, and heating to 90-110 ℃ until the rosin is completely dissolved to obtain a rosin solution;
the rosin is at least one of gum rosin, wood rosin and dehydroabietic acid;
the mass ratio of the environment-friendly solvent to the rosin is 0.5-6: 1.
4. the production method according to any one of claims 1 to 3, characterized in that: in step S2, the inorganic copper salt is at least one of basic copper carbonate, copper hydroxide and copper acetate.
5. The production method according to any one of claims 1 to 4, characterized in that: in the step S2, the reaction temperature is 120-150 ℃ and the reaction time is 1-3 h;
the mass ratio of the inorganic copper salt to the rosin is 0.1-0.5: 1.
6. the production method according to claim 4 or 5, characterized in that: in step S2, when the inorganic copper salt is basic copper carbonate or copper hydroxide, the method further comprises a step of adding acetic acid;
the mass ratio of the inorganic copper salt to the acetic acid is 0.5-2: 1.
7. the production method according to any one of claims 1 to 6, characterized in that: in step S2, distilling at 100-140 ℃; the mass percentage of the copper abietate in the copper abietate mother liquor is 15-65%.
8. The production method according to any one of claims 1 to 7, characterized in that: in step S3, the emulsifier is at least one of fatty alcohol polyoxyethylene ether, alkylphenol ethoxylate, castor oil polyoxyethylene ether, phenethyl phenol polyoxyethylene polyoxypropylene block polyether, polyoxyethylene ether sulfate, fatty alcohol ether phosphate, aryl phenol ether phosphate, and alkyl polyether phosphate potassium salt;
the antifreezing agent is at least one of ethylene glycol, propylene glycol and glycerol.
9. The production method according to any one of claims 1 to 7, characterized in that: in step S3, the copper abietate emulsion in water comprises the following components in percentage by mass:
20-60% of copper abietate mother liquor, 3-10% of emulsifier, 3-5% of antifreezing agent and the balance of water.
10. An aqueous copper abietate emulsion prepared by the process of any one of claims 1 to 9.
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| CN1147898A (en) * | 1996-07-19 | 1997-04-23 | 黄迪辉 | Method for preparing organic copper, a kind of broad-spectrum germicide |
| CN1161780A (en) * | 1996-10-16 | 1997-10-15 | 黄迪辉 | High-effective copploid liquid and preparation method thereof |
| CN101935275A (en) * | 2009-06-29 | 2011-01-05 | 孔波 | Preparation method and application of gum rosin acid copper |
| CN103497101A (en) * | 2013-10-11 | 2014-01-08 | 广东植物龙生物技术有限公司 | Preparation method and application of resin acid copper salt synthesized by aqueous phase process |
| CN103493805A (en) * | 2013-10-11 | 2014-01-08 | 广东植物龙生物技术有限公司 | Copper rosinate suspending agent and preparation method thereof |
| CN104478705A (en) * | 2014-11-11 | 2015-04-01 | 柳州市惠农化工有限公司 | Copper abietate raw drug and preparation method and application thereof |
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2021
- 2021-01-11 CN CN202110029932.9A patent/CN112674093B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147898A (en) * | 1996-07-19 | 1997-04-23 | 黄迪辉 | Method for preparing organic copper, a kind of broad-spectrum germicide |
| CN1161780A (en) * | 1996-10-16 | 1997-10-15 | 黄迪辉 | High-effective copploid liquid and preparation method thereof |
| CN101935275A (en) * | 2009-06-29 | 2011-01-05 | 孔波 | Preparation method and application of gum rosin acid copper |
| CN103497101A (en) * | 2013-10-11 | 2014-01-08 | 广东植物龙生物技术有限公司 | Preparation method and application of resin acid copper salt synthesized by aqueous phase process |
| CN103493805A (en) * | 2013-10-11 | 2014-01-08 | 广东植物龙生物技术有限公司 | Copper rosinate suspending agent and preparation method thereof |
| CN104478705A (en) * | 2014-11-11 | 2015-04-01 | 柳州市惠农化工有限公司 | Copper abietate raw drug and preparation method and application thereof |
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