CN110540638A - Preparation method of emulsifier and application of emulsifier in preparation of pesticide emulsifiable concentrate - Google Patents
Preparation method of emulsifier and application of emulsifier in preparation of pesticide emulsifiable concentrate Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
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Abstract
The invention has provided a preparation method of emulsifier and its use in preparing pesticide emulsifiable concentrate, the invention has also provided the compound emulsifier comprising this emulsifier, the above-mentioned preparation method includes, S1, regard straight chain alkane alcohol as the initiator, under the catalysis of bimetallic catalyst, add the mixture of epoxypropane and epoxybutane and react, get the polymer midbody; s2, carrying out end capping reaction on the polymer intermediate and ethylene oxide under the action of an alkali catalyst, and adding a neutralizer for neutralization to obtain an emulsifier; the mass ratio of the propylene oxide to the butylene oxide is 0.1-1.2, the addition sequence of the components is limited, the mass ratio of the propylene oxide to the butylene oxide is 0.1-1.2, and a specific auxiliary agent is selected for compounding, so that the emulsifying agent has good emulsifying and dispersing effects, can be stably stored for a long time, and needs less emulsifying agent and organic solvent when preparing the pesticide emulsifiable concentrate, and is more economic and environment-friendly.
Description
Technical Field
the invention relates to the technical field of emulsifiers, in particular to a preparation method of an emulsifier and application of the emulsifier in preparation of pesticide emulsifiable concentrate.
Background
As a big agricultural country, China has great market demand for pesticide emulsifiable solution. The emulsifier is used as an important component in the pesticide emulsifiable concentrate, has the functions of enabling the pesticide emulsifiable concentrate to stably exist for a long time without generating flocculent precipitates, can effectively reduce the surface tension by adding water for dilution when being used in agricultural production, obviously increases the functions of wetting, emulsifying, dispersing, permeating and the like, enhances the spreading and adhesion on plants and further improves the efficacy of the pesticide.
The emulsifying effect of the nonionic emulsifier depends on a hydrophilic group and a hydrophobic group with a proper proportion, and the conventional reaction mechanism is that Propylene Oxide (PO) and Ethylene Oxide (EO) are polymerized according to a certain proportion to obtain a product.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the emulsifying agent prepared by the emulsifying agent preparation method in the prior art has poor emulsifying and dispersing effects, cannot be stably stored for a long time and has large addition amount of the emulsifying agent and the organic solvent, thereby providing an economic and environment-friendly emulsifying agent preparation method which has good emulsifying and dispersing effects, can be stably stored for a long time and has small amount of the required emulsifying agent and the required organic solvent, and the application of the emulsifying agent in preparation of pesticide emulsifiable concentrate.
Therefore, the invention provides a preparation method of the emulsifier, which comprises the following steps,
S1, adding a mixture of propylene oxide and butylene oxide to react under the catalysis of a bimetallic catalyst by using straight-chain alkane alcohol as an initiator to obtain a polymer intermediate;
S2, carrying out end capping reaction on the polymer intermediate and ethylene oxide under the action of an alkali catalyst, and adding a neutralizer for neutralization to obtain an emulsifier;
Wherein the mass ratio of the propylene oxide to the butylene oxide is 0.1-1.2, preferably 0.3-0.8.
The preparation method of the emulsifier comprises the following steps of (1.2-1.8): 1.
In the step S1, the initiator includes one or more of propanol, n-butanol, n-pentanol, or n-hexanol.
In the step S1, the bimetallic catalyst is a zinc-cobalt bimetallic cyanide complex catalyst; the mass of the bimetallic catalyst is 0.001-0.009%, preferably 0.0015-0.006% of the mass of the polymer intermediate.
in the step S2, the alkali catalyst comprises one or more of potassium hydroxide, sodium or sodium hydride; the mass of the alkali catalyst is 0.05-0.8%, preferably 0.1-0.5% of the mass of the emulsifier.
The preparation method of the emulsifier, in the step S1, the reaction temperature is 120-180 ℃, preferably 140-160 ℃.
in the step S2, the temperature of the capping reaction is 110-150 ℃, preferably 120-130 ℃.
In the preparation method of the emulsifier, in the step S2, the neutralizing agent is one or more of acetic acid, lactic acid and citric acid, the neutralizing temperature is 60-100 ℃, and the pH value after neutralization is 4-8, preferably 5-7.
the HLB value of the emulsifier is 13-21.
the invention provides a composite emulsifier, which comprises the emulsifier prepared by the method and an auxiliary agent, wherein the auxiliary agent is a mixture of calcium dodecyl benzene sulfonate, sodium dodecyl sulfate and alkylphenol ethoxylates;
Based on the total mass of the composite emulsifier, the content of the emulsifier is 98-99 wt%, the content of the calcium dodecyl benzene sulfonate is 0.8-1.2 wt%, the content of the sodium dodecyl sulfate is 0.1-0.2 wt%, and the content of the alkylphenol polyoxyethylene ether is 0.1-0.6 wt%.
The invention also provides the use of the emulsifier obtained by the preparation method of the emulsifier or the composite emulsifier in the preparation of pesticide emulsifiable concentrate.
The emulsifier obtained by the preparation method of the emulsifier or the composite emulsifier is used for preparing pesticide emulsifiable concentrate, wherein the emulsifier or the composite emulsifier accounts for 3-7% of the pesticide emulsifiable concentrate by mass.
The technical scheme of the invention has the following advantages:
1. The preparation method of the emulsifier provided by the invention comprises the steps of S1, adding a mixture of Propylene Oxide (PO) and Butylene Oxide (BO) to react under the catalysis of a bimetallic catalyst by using straight-chain alkane alcohol as an initiator to obtain a polymer intermediate; s2, carrying out end capping reaction on the polymer intermediate and Ethylene Oxide (EO) under the action of an alkali catalyst, and adding a neutralizer for neutralization to obtain an emulsifier; wherein, the mass ratio of the Propylene Oxide (PO) to the Butylene Oxide (BO) is 0.1-1.2, the method adopts straight-chain alkane alcohol as an initiator, and the emulsifier has small viscosity, good fluidity, strong emulsifying effect and excellent permeability due to the adoption of a flexible chain, thereby more effectively exerting the pesticide effect of the pesticide; by adopting different catalysts in the S1 step and the S2 step, the occurrence of side reactions can be reduced, so that the selectivity of the polymerization reaction is better, the product purity is high, and the performance is excellent; BO with stronger lipophilicity is introduced into a molecular chain, so that the emulsifier has stronger binding capacity with a raw pesticide, higher stability in a solvent and better low-temperature fluidity; EO in the molecular chain has better hydrophilic effect, so that the emulsifiable solution prepared by the emulsifier can be quickly dispersed in water, has better dispersion effect and can keep transparent emulsion for a long time; the lipophilic groups are modified by limiting the adding sequence of the components and the mass ratio of PO to BO to be 0.1-1.2, so that the obtained emulsifier has good emulsifying and dispersing effects and can be stably stored for a long time, and the required amount of the emulsifier and the organic solvent is less when pesticide emulsifiable concentrate is prepared, thereby being more economic and environment-friendly.
2. According to the preparation method of the emulsifier provided by the invention, the mass ratio of the mixture of the propylene oxide and the butylene oxide to the ethylene oxide is (1.2-1.8): 1, by limiting the mass ratio of the mixture of PO and BO to EO, the proportion of lipophilic groups to hydrophilic groups in the emulsifier can be optimized, so that the emulsifying and dispersing effects of the emulsifier are optimized, the stability of the emulsifier is improved, and the emulsifier and the organic solvent are less in required amount and are more economical and environment-friendly when the pesticide emulsifiable concentrate is prepared.
3. According to the preparation method of the emulsifier provided by the invention, in the step S1, the initiator comprises one or more of propanol, n-butanol, n-amyl alcohol or n-hexyl alcohol, and the linear alkane alcohols are used as the initiator, so that the obtained emulsifier has the advantages of small viscosity, good fluidity, strong emulsifying effect and excellent permeability, and can more effectively exert the pesticide effect of the pesticide.
4. In the preparation method of the emulsifier provided by the invention, in the step S1, the bimetallic catalyst is a zinc-cobalt bimetallic cyanide complex catalyst; the mass of the bimetallic catalyst is 0.001-0.009% of the mass of the polymer intermediate, and by adopting the zinc-cobalt bimetallic cyanide complex catalyst and limiting the dosage of the catalyst, the occurrence of side reactions can be reduced, so that the selectivity of polymerization reaction is better, the product purity is high, and the polymer intermediate with narrower molecular weight distribution coefficient and excellent performance is obtained.
5. in the preparation method of the emulsifier provided by the invention, in the step S2, the alkali catalyst comprises one or more of potassium hydroxide, sodium or sodium hydride; the mass of the alkali catalyst is 0.05-0.8% of that of the emulsifier, and by adopting the alkali catalysts, the end capping reaction can be promoted, other side reactions can be reduced, and the product has high purity and excellent performance.
6. According to the preparation method of the emulsifier, in the step S1, the reaction temperature is 120-180 ℃, because the bimetallic catalyst is adopted to prepare the polymer intermediate in the step S1, the required reaction temperature is higher, and the side reaction can be reduced by limiting the reaction temperature to 120-180 ℃, so that the product with narrow molecular weight distribution coefficient and excellent performance is obtained.
7. According to the preparation method of the emulsifier, in the step S2, the temperature of the end capping reaction is 110-150 ℃, in the step S2, when the EO is subjected to the end capping reaction, an alkali catalyst is used, the EO does not react due to too low temperature, and the EO self-polymerization and the byproducts are increased due to too high temperature, and by limiting the temperature of the end capping reaction to be 110-150 ℃, the byproducts can be reduced while the smooth reaction is ensured, so that the product with narrow molecular weight distribution coefficient and excellent performance is obtained.
8. According to the preparation method of the emulsifier, in the step S2, the neutralizing agent is one or more of acetic acid, lactic acid and citric acid, the neutralizing temperature is 60-100 ℃, the pH value after neutralization is 4-8, the alkali catalyst can be neutralized by adopting the neutralizing agent, and the product is prevented from changing color and affecting the quality due to overhigh temperature by limiting the neutralizing temperature to be 60-100 ℃.
9. The composite emulsifier provided by the invention comprises the emulsifier prepared by the method and an auxiliary agent, wherein the auxiliary agent is a mixture of calcium dodecyl benzene sulfonate, sodium dodecyl sulfate and alkylphenol ethoxylates; the composite emulsifier prepared by the method is mixed with an auxiliary agent, and has better emulsification, wetting and permeation effects and better use effects, only less organic solvent is needed, the stability of missible oil can be kept, and the pesticide effect can be efficiently exerted; by limiting the content of the emulsifier to a higher range of 98-99 wt%, on one hand, the use amount of the auxiliary agent can be reduced, so that the possibility of substance precipitation during long-term storage of the missible oil is reduced, on the other hand, the emulsification can be completed only by adding a small amount of the composite emulsifier, the use amount of an organic solvent is greatly reduced, and the environmental pollution is reduced.
10. The emulsifier or the composite emulsifier prepared by the preparation method of the emulsifier provided by the invention is used for preparing the pesticide emulsifiable concentrate, can achieve better emulsification and dispersion effects when being used for preparing the pesticide emulsifiable concentrate, can be stably stored for a long time, and is economic and environment-friendly due to the small amount of the required emulsifier and organic solvent.
Detailed Description
Example 1
This example provides a method for preparing an emulsifier comprising,
s1, taking 100kg of n-hexanol as an initiator, heating to 140 ℃ after nitrogen replacement, adding 2510kg of a mixture of propylene oxide and butylene oxide under the catalysis of 0.13kg of zinc-cobalt double metal cyanide complex catalyst to react, wherein the mass ratio of the propylene oxide to the butylene oxide is 0.6, the reaction temperature is 140 ℃, and curing and degassing to obtain a polymer intermediate.
S2, carrying out end capping reaction on the polymer intermediate obtained in the step S1 and 1673kg of ethylene oxide under the action of 18.4kg of sodium hydride, wherein the end capping reaction temperature is 120 ℃, carrying out curing and degassing, cooling to 70 ℃, adding lactic acid for neutralization, and the pH value is 6 after neutralization to finally obtain 4283kg of emulsifier.
the embodiment also provides the application of the emulsifier prepared by the method in preparing pesticide emulsifiable solution, wherein 65kg of fenoxanil, 30kg of dimethylbenzene and 5kg of emulsifier are mixed to obtain the fenoxanil pesticide emulsifiable solution, the low-temperature stability and the heat storage stability of the pesticide emulsifiable solution are respectively measured by adopting a GB/T19136-2003-doped pesticide heat storage stability measuring method and a GB/T19137-doped 2003-pesticide low-temperature stability measuring method, and the prepared pesticide emulsifiable solution can be kept uniform and stable, has no precipitation and crystallization, is rapidly and automatically uniform when entering water and is light white transparent emulsion after being stirred at a specified temperature and within a specified time.
Example 2
This example provides a method for preparing an emulsifier comprising,
S1, putting 100kg of propanol serving as an initiator and 0.06kg of zinc-cobalt double metal cyanide together into a reaction kettle in a complex catalysis manner, heating to 120 ℃ after nitrogen replacement, adding 4230kg of a mixture of propylene oxide and butylene oxide into the reaction kettle for reaction, wherein the mass ratio of the propylene oxide to the butylene oxide is 0.1, the reaction temperature is 120 ℃, and curing and degassing to obtain a polymer intermediate.
S2, adding 4kg of metal sodium catalyst into the reaction kettle, carrying out end capping reaction on the polymer intermediate obtained in the step S1 and 3490kg of ethylene oxide under the catalytic action of the metal sodium, wherein the end capping reaction temperature is 110 ℃, carrying out curing degassing, cooling to 60 ℃, adding acetic acid for neutralization, and the pH value is 7 after neutralization to finally obtain 7820kg of emulsifier.
The embodiment also provides a composite emulsifier, which comprises the emulsifier obtained by the method and an auxiliary agent, wherein the auxiliary agent is a mixture of calcium dodecyl benzene sulfonate, sodium dodecyl sulfate and alkylphenol ethoxylates; based on the total mass of the composite emulsifier, the content of the emulsifier is 99 wt%, the content of calcium dodecyl benzene sulfonate is 0.8 wt%, the content of sodium dodecyl sulfate is 0.1 wt%, and the content of alkylphenol polyoxyethylene is 0.1 wt%.
The embodiment also provides the application of the composite emulsifier in the preparation of pesticide emulsifiable solution, 68kg of fenitrothion, 27kg of xylene and 5kg of the composite emulsifier are mixed to obtain the fenitrothion pesticide emulsifiable solution, the low-temperature stability and the thermal storage stability of the pesticide emulsifiable solution are measured by respectively adopting a GB/T19136-2003-containing pesticide thermal storage stability measuring method and a GB/T19137-containing 2003-containing pesticide low-temperature stability measuring method, the prepared pesticide emulsifiable solution can be kept uniform and stable at a specified temperature and within a specified time, is free of precipitation and crystallization, is rapidly and automatically uniform when entering water, and is in a light white transparent emulsion after being stirred.
Example 3
This example provides a method for preparing an emulsifier comprising,
s1, putting 100kg of n-butyl alcohol as an initiator and 0.31kg of zinc-cobalt double metal cyanide together into a reaction kettle in a complex catalysis manner, heating to 180 ℃ after nitrogen replacement, adding 3370kg of a mixture of propylene oxide and butylene oxide into the reaction kettle for reaction, wherein the mass ratio of the propylene oxide to the butylene oxide is 1.2, the reaction temperature is 180 ℃, and curing and degassing to obtain a polymer intermediate.
S2, adding 42.7kg of sodium hydroxide catalyst into a reaction kettle, carrying out end capping reaction on the polymer intermediate obtained in the step S1 and 1872kg of ethylene oxide under the catalytic action of sodium hydroxide, wherein the end capping reaction temperature is 150 ℃, carrying out curing and degassing, cooling to 100 ℃, adding citric acid for neutralization, and the pH value is 5 after neutralization to finally obtain 5342kg of emulsifier.
The embodiment also provides a composite emulsifier, which comprises the emulsifier obtained by the method and an auxiliary agent, wherein the auxiliary agent is a mixture of calcium dodecyl benzene sulfonate, sodium dodecyl sulfate and alkylphenol ethoxylates; based on the total mass of the composite emulsifier, the content of the emulsifier is 98 wt%, the content of calcium dodecyl benzene sulfonate is 1.2 wt%, the content of sodium dodecyl sulfate is 0.2 wt%, and the content of alkylphenol polyoxyethylene is 0.6 wt%.
The embodiment also provides the application of the composite emulsifier in the preparation of pesticide emulsifiable solution, 60kg of phenthoate, 34kg of dimethylbenzene and 6kg of composite emulsifier are mixed to obtain the phenthoate pesticide emulsifiable solution, the GB/T19136-2003-pesticide heat storage stability determination method and the GB/T19137-2003-pesticide low-temperature stability determination method are respectively adopted to determine the low-temperature stability and the heat storage stability of the pesticide emulsifiable solution, the prepared pesticide emulsifiable solution can be kept uniform and stable within the specified temperature and time, is free of precipitation and crystallization, is rapidly and automatically uniform when entering water, and is light white transparent emulsion after being stirred.
Example 4
this example provides a method for preparing an emulsifier comprising,
S1, adding 100kg of n-amyl alcohol serving as an initiator into a reaction kettle together with 0.13kg of zinc-cobalt double metal cyanide through complex catalysis, heating to 140 ℃ after nitrogen replacement, adding 2510kg of a mixture of epoxypropane and epoxybutane into the reaction kettle for reaction, wherein the mass ratio of the epoxypropane to the epoxybutane is 0.6, the reaction temperature is 140 ℃, and curing and degassing to obtain a polymer intermediate.
S2, adding 18.4kg of potassium hydroxide catalyst into a reaction kettle, carrying out end capping reaction on the polymer intermediate obtained in the step S1 and 1673kg of ethylene oxide under the catalytic action of potassium hydroxide, wherein the end capping reaction temperature is 120 ℃, carrying out curing degassing, cooling to 70 ℃, adding lactic acid for neutralization, and the pH value is 6 after neutralization to finally obtain 4283kg of emulsifier.
The embodiment also provides a composite emulsifier, which comprises the emulsifier obtained by the method and an auxiliary agent, wherein the auxiliary agent is a mixture of calcium dodecyl benzene sulfonate, sodium dodecyl sulfate and alkylphenol ethoxylates; based on the total mass of the composite emulsifier, the content of the emulsifier is 98.5 wt%, the content of calcium dodecyl benzene sulfonate is 0.9 wt%, the content of sodium dodecyl sulfate is 0.2 wt%, and the content of alkylphenol polyoxyethylene is 0.4 wt%.
The embodiment also provides the application of the composite emulsifier in the preparation of pesticide emulsifiable solution, wherein 65kg of fenoxanil, 30kg of dimethylbenzene and 5kg of the composite emulsifier are mixed to obtain the fenoxanil pesticide emulsifiable solution, the low-temperature stability and the thermal storage stability of the pesticide emulsifiable solution are respectively measured by adopting a GB/T19136-2003-pesticide thermal storage stability measuring method and a GB/T19137-2003-pesticide low-temperature stability measuring method, the prepared pesticide emulsifiable solution can be uniformly and stably kept at a specified temperature and within a specified time, is free of precipitation and crystallization, is rapidly and automatically uniform when entering water, and is in a light white transparent emulsion after being stirred.
Comparative example 1
this comparative example provides a method for producing an emulsifier, which is similar to that of example 4 except that the mass ratio of propylene oxide to butylene oxide in the step of S1 is 0.05. Mixing 41kg of pyricularia oryzae, 50kg of dimethylbenzene and 9kg of composite emulsifier to obtain pyricularia oryzae pesticide emulsifiable solution, and respectively adopting a GB/T19136-2003 pesticide heat storage stability determination method and a GB/T19137-2003 pesticide low temperature stability determination method to determine the low temperature stability and the heat storage stability of the pesticide emulsifiable solution, wherein the pesticide emulsifiable solution is layered and crystallized and precipitated in an oil bead shape when entering water, and is a blue opaque emulsion after being stirred.
Comparative example 2
This comparative example provides a method for producing an emulsifier, which is similar to that of example 4 except that in the step of S1, the mass ratio of propylene oxide to butylene oxide is 2. Mixing 41kg of pyricularia oryzae, 50kg of dimethylbenzene and 9kg of composite emulsifier to obtain pyricularia oryzae pesticide emulsifiable solution, and respectively adopting a GB/T19136-2003 pesticide heat storage stability determination method and a GB/T19137-2003 pesticide low temperature stability determination method to determine the low temperature stability and the heat storage stability of the pesticide emulsifiable solution, wherein the pesticide emulsifiable solution is layered and crystallized and precipitated in an oil bead shape when entering water, and is a blue opaque emulsion after being stirred.
Comparative example 3
The comparative example adopts a commercial nonionic emulsifier from Acksonobel to prepare the fenoxanil pesticide emulsifiable solution, 41kg of fenoxanil, 50kg of dimethylbenzene and 9kg of a commercial nonionic emulsifier are used to obtain the fenoxanil pesticide emulsifiable solution, and a GB/T19136-2003 pesticide thermal storage stability determination method and a GB/T19137-2003 pesticide low-temperature stability determination method are respectively adopted to determine the low-temperature stability and the thermal storage stability of the pesticide emulsifiable solution, so that layering and crystallization precipitation respectively occur, the emulsifiable solution sinks in an oil bead shape when entering water, and the emulsifiable solution is blue opaque emulsion after stirring.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A preparation method of an emulsifier is characterized by comprising the following steps,
S1, adding a mixture of propylene oxide and butylene oxide to react under the catalysis of a bimetallic catalyst by using straight-chain alkane alcohol as an initiator to obtain a polymer intermediate;
s2, carrying out end capping reaction on the polymer intermediate and ethylene oxide under the action of an alkali catalyst, and adding a neutralizer for neutralization to obtain an emulsifier;
wherein the mass ratio of the propylene oxide to the butylene oxide is 0.1-1.2.
2. The process for the preparation of the emulsifier according to claim 1, wherein the mass ratio of the mixture of propylene oxide and butylene oxide to the ethylene oxide is (1.2-1.8): 1.
3. The method for preparing the emulsifier according to claim 1 or 2, wherein in the step of S1, the initiator comprises one or more of propanol, n-butanol, n-pentanol or n-hexanol.
4. The method for preparing an emulsifier according to any one of claims 1 to 3, wherein in the step S1, the double metal catalyst is a zinc-cobalt double metal cyanide complex catalyst; the mass of the bimetallic catalyst is 0.001-0.009% of the mass of the polymer intermediate.
5. The method for preparing the emulsifier according to any one of claims 1 to 4, wherein in the step S2, the alkali catalyst comprises one or more of potassium hydroxide, sodium or sodium hydride; the mass of the alkali catalyst is 0.05-0.8% of that of the emulsifier.
6. The method for preparing an emulsifier according to any one of claims 1 to 5, wherein the reaction temperature in the step S1 is 120-180 ℃.
7. The method for preparing an emulsifier according to any one of claims 1 to 6, wherein the temperature of the capping reaction in the step S2 is 110-150 ℃.
8. the method for preparing the emulsifier according to any one of claims 1 to 7, wherein in the step S2, the neutralizing agent is one or more of acetic acid, lactic acid and citric acid, the neutralizing temperature is 60 to 100 ℃, and the pH value after neutralization is 4 to 8.
9. A composite emulsifier, which is characterized by comprising the emulsifier prepared by the method of any one of claims 1 to 8 and an auxiliary agent, wherein the auxiliary agent is a mixture of calcium dodecyl benzene sulfonate, sodium dodecyl sulfate and alkylphenol ethoxylates;
based on the total mass of the composite emulsifier, the content of the emulsifier is 98-99 wt%, the content of the calcium dodecyl benzene sulfonate is 0.8-1.2 wt%, the content of the sodium dodecyl sulfate is 0.1-0.2 wt%, and the content of the alkylphenol polyoxyethylene ether is 0.1-0.6 wt%.
10. Use of the emulsifier obtained by the method for preparing the emulsifier according to any one of claims 1 to 8 or the composite emulsifier according to claim 9 for preparing a pesticidal emulsifiable concentrate.
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