Disclosure of Invention
In order to improve the long-acting performance of the anti-dripping agent, the application provides a long-acting anti-dripping agent component and a production process.
In a first aspect, the present application provides a long-acting drip agent component, which adopts the following technical scheme:
The long-acting drip agent comprises, by weight, 10-20 parts of polyethylene oxide, 5-15 parts of fatty alcohol polyoxyethylene ether, 3-8 parts of silicone oil, 2-6 parts of a surfactant and 1-3 parts of modified nano silicon dioxide, wherein the raw materials of the modified nano silicon dioxide comprise nano silicon dioxide, kaolin, glycerol monostearate monoacrylic acid diester, sucrose fatty acid ester and azodiisobutyronitrile.
By adopting the technical scheme, the glycerin monostearate and the sucrose fatty acid ester are utilized to modify the nano silicon dioxide and the kaolin, so that the dispersion performance of the modified nano silicon dioxide is improved, the stability and the adhesive force of the drip agent are also improved, the release speed of the drip agent is controlled, the durability of the drip agent is improved by polyethylene oxide, the wettability and the dispersibility of the drip agent are enhanced by fatty alcohol polyoxyethylene ether, and the leveling property and the heat resistance of the drip agent are improved by silicone oil, so that the long-acting property of the drip agent component is improved by the cooperation of the glycerin monostearate and the sucrose fatty acid ester.
In a specific embodiment, the method for preparing the modified nano-silica comprises the following steps:
The preparation method comprises the steps of pre-treating, namely stirring and mixing gamma-aminopropyl triethoxysilane, ethanol and water uniformly to obtain a spraying liquid, stirring and mixing nano silicon dioxide and kaolin uniformly to obtain a mixture, spraying the spraying liquid into the mixture in the stirring process, continuing stirring after spraying, and drying to obtain the pre-treated silicon dioxide;
And modifying, namely heating and melting glycerin monostearate and sucrose fatty acid ester, adding pretreated silicon dioxide and azodiisobutyronitrile, reacting under the protection of nitrogen, washing and drying the obtained product, and thus obtaining the modified nano silicon dioxide.
By adopting the technical scheme, the gamma-aminopropyl triethoxysilane is utilized to pretreat the nano silicon dioxide and the kaolin, so that the dispersion performance of the nano silicon dioxide and the kaolin is improved, and then the nano silicon dioxide is grafted and modified under the initiation of the azobisisobutyronitrile, so as to obtain the modified nano silicon dioxide.
In a specific embodiment, in the pretreatment step, the weight ratio of the spray liquid to the mixture is 1 (13-14).
In a specific embodiment, the weight ratio of glycerol monostearate to sucrose fatty acid ester, pretreated silica, azodiisobutyronitrile in the modifying step is (125-135): 25-35): 20:1.
By adopting the technical scheme, the proportion of the spraying liquid to the mixture and the proportion of the glycerol monostearate monoacrylate, the sucrose fatty acid ester, the pretreated silicon dioxide and the azodiisobutyronitrile are further limited, so that the modification effect on the nano silicon dioxide is improved.
In a specific embodiment, the method of preparing the surfactant comprises the steps of:
The monoglyceride, the 2-methylene succinic anhydride, the 4-methylbenzenesulfonic acid and the 1, 4-benzenediol are heated, stirred and dissolved, then heated, reacted and refluxed, cooled to obtain a reactant, then sodium dodecyl benzene sulfonate is added, and the mixture is stirred and mixed uniformly to obtain the surfactant.
By adopting the technical scheme, the monoglyceride, the 2-methylene succinic anhydride, the 4-methylbenzenesulfonic acid and the 1, 4-benzenediol are firstly reacted, and the obtained reactant is mixed with the sodium dodecyl benzene sulfonate, so that the obtained surfactant has emulsifying capacity and stability, and the dripping effect of the dripping agent can be improved.
In a specific embodiment, the molar ratio of the monoglyceride, the 2-methylenesuccinic anhydride, the 4-methylbenzenesulfonic acid, and the 1, 4-benzenediol is 1 (0.97-0.99): (0.084-0.086): (0.006-0.008).
By adopting the technical scheme, the proportion of the monoglyceride, the 2-methylene succinic anhydride, the 4-methylbenzenesulfonic acid and the 1, 4-benzenediol is further limited, and the performance of the obtained surfactant can be further improved.
In a specific embodiment, the silicone oil has a viscosity of 500 to 1000 centipoise.
By adopting the technical scheme, when the viscosity of the silicone oil is 500-1000 centipoises, the fluidity and the stability of the components of the drip agent can be effectively improved, thereby prolonging the action time of the drip agent.
In a specific embodiment, the raw materials of the long-acting drip agent component further comprise 0.1-1 parts by weight of an antioxidant, wherein the antioxidant comprises one or more of ascorbic acid, butylhydroxytoluene and thiodipropionate.
In a specific embodiment, the raw materials of the long-acting drip agent component further comprise 0.1-1 parts by weight of an ultraviolet absorbent, wherein the ultraviolet absorbent comprises one or more of a salicylate absorbent, a benzophenone absorbent and a benzotriazole absorbent.
In a second aspect, the application provides a production process of a long-acting drip agent component, which adopts the following technical scheme:
a process for producing a long-acting drip formulation comprising the steps of:
and uniformly stirring and mixing polyethylene oxide, fatty alcohol polyoxyethylene ether, silicone oil, a surfactant and modified nano silicon dioxide to obtain a long-acting drip agent component.
By adopting the technical scheme, polyethylene oxide, fatty alcohol polyoxyethylene ether, silicone oil, surfactant and modified nano silicon dioxide are stirred and mixed uniformly to obtain the long-acting drip agent component with longer action effect.
In summary, the present application includes at least one of the following beneficial technical effects:
1. According to the application, the glycerin monostearate and the sucrose fatty acid ester are used for modifying the nano silicon dioxide and the kaolin, so that the dispersion property of the modified nano silicon dioxide is improved, the stability and the adhesive force of the drip agent are also improved, and the release speed of the drip agent is controlled;
2. in the application, gamma-aminopropyl triethoxysilane is utilized to pretreat nano silicon dioxide and kaolin, so that the dispersion performance of the nano silicon dioxide and the kaolin is improved, and then the nano silicon dioxide is grafted and modified under the initiation of azodiisobutyronitrile to obtain modified nano silicon dioxide;
3. according to the process, polyethylene oxide, fatty alcohol polyoxyethylene ether, silicone oil, a surfactant and modified nano silicon dioxide are stirred and mixed uniformly to obtain a long-acting drip agent component with a longer acting effect.
Detailed Description
The present application will be described in further detail with reference to examples.
All the starting materials in the examples are commercially available. Wherein the antioxidant comprises a mixture of one or more of ascorbic acid, butylhydroxytoluene and thiodipropionate, the butylhydroxytoluene is preferred in the present application, and the ultraviolet absorbent comprises a mixture of one or more of salicylate absorbent, benzophenone absorbent and benzotriazole absorbent, and the salicylate absorbent phenyl salicylate is preferred in the present application.
Preparation example
Preparation example 1
Preparation example 1 provides a preparation method of modified nano silicon dioxide, which comprises the following steps:
The preparation method comprises the steps of pre-treating, namely stirring and mixing gamma-aminopropyl triethoxysilane, ethanol and water uniformly to obtain a spraying liquid, stirring and mixing nano silicon dioxide and kaolin uniformly to obtain a mixture, slowly spraying the spraying liquid into the mixture in the stirring process, continuously stirring for 0.5h after the spraying is finished, and drying at 80 ℃ for 0.5h to obtain the pre-treated silicon dioxide, wherein the weight ratio of the gamma-aminopropyl triethoxysilane to the ethanol to the water is 5:18:2, the weight ratio of the nano silicon dioxide to the kaolin in the mixture is 5:1, and the weight ratio of the spraying liquid to the mixture is 1:13;
And (3) modifying, namely heating and melting the glycerin monostearate and the sucrose fatty acid ester in a water bath at a temperature of 85 ℃, adding the pretreated silicon dioxide and the azodiisobutyronitrile, reacting for 8 hours under the protection of nitrogen, and washing and drying the obtained product to obtain the modified nano silicon dioxide, wherein the weight ratio of the glycerin monostearate to the sucrose fatty acid ester to the pretreated silicon dioxide to the azodiisobutyronitrile is 125:25:20:1.
Preparation example 2
Preparation example 2 provides a preparation method of modified nano silicon dioxide, which comprises the following steps:
The preparation method comprises the steps of pre-treating, namely stirring and mixing gamma-aminopropyl triethoxysilane, ethanol and water uniformly to obtain a spraying liquid, stirring and mixing nano silicon dioxide and kaolin uniformly to obtain a mixture, slowly spraying the spraying liquid into the mixture in the stirring process, continuously stirring for 0.5h after the spraying is finished, and drying at 80 ℃ for 0.5h to obtain the pre-treated silicon dioxide, wherein the weight ratio of the gamma-aminopropyl triethoxysilane to the ethanol to the water is 5:18:2, the weight ratio of the nano silicon dioxide to the kaolin in the mixture is 5:1, and the weight ratio of the spraying liquid to the mixture is 1:13.5;
And (3) modifying, namely heating and melting the glycerin monostearate and the sucrose fatty acid ester in a water bath at a temperature of 85 ℃, adding the pretreated silicon dioxide and the azodiisobutyronitrile, reacting for 8 hours under the protection of nitrogen, and washing and drying the obtained product to obtain the modified nano silicon dioxide, wherein the weight ratio of the glycerin monostearate to the sucrose fatty acid ester to the pretreated silicon dioxide to the azodiisobutyronitrile is 130:30:20:1.
Preparation example 3
Preparation example 3 provides a preparation method of modified nano silicon dioxide, which comprises the following steps:
The preparation method comprises the steps of pre-treating, namely stirring and mixing gamma-aminopropyl triethoxysilane, ethanol and water uniformly to obtain a spraying liquid, stirring and mixing nano silicon dioxide and kaolin uniformly to obtain a mixture, slowly spraying the spraying liquid into the mixture in the stirring process, continuously stirring for 0.5h after the spraying is finished, and drying at 80 ℃ for 0.5h to obtain the pre-treated silicon dioxide, wherein the weight ratio of the gamma-aminopropyl triethoxysilane to the ethanol to the water is 5:18:2, the weight ratio of the nano silicon dioxide to the kaolin in the mixture is 5:1, and the weight ratio of the spraying liquid to the mixture is 1:14;
And modifying, namely heating and melting the glycerin monostearate and the sucrose fatty acid ester in a water bath at the temperature of 85 ℃, adding the pretreated silicon dioxide and the azodiisobutyronitrile, reacting for 8 hours under the protection of nitrogen, and washing and drying the obtained product to obtain the modified nano silicon dioxide, wherein the weight ratio of the glycerin monostearate to the sucrose fatty acid ester to the pretreated silicon dioxide to the azodiisobutyronitrile is 135:35:20:1.
Preparation example 4
Preparation example 4 provides a preparation method of a surfactant, which comprises the following steps:
Heating monoglyceride, 2-methylene succinic anhydride, 4-methylbenzenesulfonic acid and 1, 4-benzenediol to 90 ℃, stirring for dissolution, heating to 100 ℃ for reaction reflux for 5 hours, cooling supernatant to obtain a reactant, adding sodium dodecyl benzene sulfonate, stirring and mixing uniformly to obtain a surfactant, wherein the mol ratio of monoglyceride to 2-methylene succinic anhydride to 4-methylbenzenesulfonic acid to 1, 4-benzenediol is 1:0.97:0.084:0.006, and the weight ratio of the reactant to sodium dodecyl benzene sulfonate is 4:1.
Preparation example 5
Preparation example 5 provides a preparation method of a surfactant, which comprises the following steps:
Heating monoglyceride, 2-methylene succinic anhydride, 4-methylbenzenesulfonic acid and 1, 4-benzenediol to 90 ℃, stirring for dissolution, heating to 100 ℃ for reaction reflux for 5 hours, cooling supernatant to obtain a reactant, adding sodium dodecyl benzene sulfonate, stirring and mixing uniformly to obtain a surfactant, wherein the mol ratio of monoglyceride to 2-methylene succinic anhydride to 4-methylbenzenesulfonic acid to 1, 4-benzenediol is 1:0.98:0.085:0.007, and the weight ratio of the reactant to sodium dodecyl benzene sulfonate is 4:1.
Preparation example 6
Preparation example 6 provides a preparation method of a surfactant, which comprises the following steps:
Heating monoglyceride, 2-methylene succinic anhydride, 4-methylbenzenesulfonic acid and 1, 4-benzenediol to 90 ℃, stirring for dissolution, heating to 100 ℃ for reaction reflux for 5 hours, cooling supernatant to obtain a reactant, adding sodium dodecyl benzene sulfonate, stirring and mixing uniformly to obtain a surfactant, wherein the mol ratio of monoglyceride to 2-methylene succinic anhydride to 4-methylbenzenesulfonic acid to 1, 4-benzenediol is 1:0.99:0.086:0.008, and the weight ratio of the reactant to sodium dodecyl benzene sulfonate is 4:1.
Examples
Example 1
Example 1 provides a process for the production of a long-acting drip-inhibiting agent component comprising the steps of:
10kg of polyethylene oxide, 5kg of fatty alcohol polyoxyethylene ether, 3kg of silicone oil, 2kg of surfactant in preparation example 4 and 1kg of modified nano silicon dioxide in preparation example 1 are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
Example 2
Example 2 provides a process for the production of a long-acting drip-retardant component comprising the steps of:
10kg of polyethylene oxide, 5kg of fatty alcohol polyoxyethylene ether, 3kg of silicone oil, 2kg of surfactant in preparation example 4 and 1kg of modified nano silicon dioxide in preparation example 2 are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
Example 3
Example 3 provides a process for the production of a long-acting drip-retardant component comprising the steps of:
10kg of polyethylene oxide, 5kg of fatty alcohol polyoxyethylene ether, 3kg of silicone oil, 2kg of surfactant in preparation example 4 and 1kg of modified nano silicon dioxide in preparation example 3 are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
Example 4
Example 4 provides a process for the production of a long-acting drip-retardant component comprising the steps of:
10kg of polyethylene oxide, 5kg of fatty alcohol polyoxyethylene ether, 3kg of silicone oil, 2kg of surfactant in preparation example 5 and 1kg of modified nano silicon dioxide in preparation example 2 are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
Example 5
Example 5 provides a process for the production of a long-acting drip-retardant component comprising the steps of:
10kg of polyethylene oxide, 5kg of fatty alcohol polyoxyethylene ether, 3kg of silicone oil, 2kg of surfactant in preparation example 6 and 1kg of modified nano silicon dioxide in preparation example 2 are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
Example 6
Example 6 provides a process for the production of a long-acting drip-retardant component comprising the steps of:
15kg of polyethylene oxide, 10kg of fatty alcohol polyoxyethylene ether, 5.5kg of silicone oil, 4kg of surfactant in preparation example 5 and 2kg of modified nano silicon dioxide in preparation example 2 are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
Example 7
Example 7 provides a process for the production of a long-acting drip retardant component comprising the steps of:
20kg of polyethylene oxide, 15kg of fatty alcohol polyoxyethylene ether, 8kg of silicone oil, 6kg of surfactant in preparation example 5 and 3kg of modified nano silicon dioxide in preparation example 2 are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
Example 8
Example 8 provides a process for the production of a long-acting drip retardant component comprising the steps of:
15kg of polyethylene oxide, 10kg of fatty alcohol polyoxyethylene ether, 5.5kg of silicone oil, 4kg of surfactant in preparation example 5, 2kg of modified nano silicon dioxide in preparation example 2 and 0.5kg of antioxidant are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoises, and the antioxidant is butylated hydroxytoluene.
Example 9
Example 9 provides a process for the production of a long-acting drip retardant component comprising the steps of:
15kg of polyethylene oxide, 10kg of fatty alcohol polyoxyethylene ether, 5.5kg of silicone oil, 4kg of surfactant in preparation example 5, 2kg of modified nano silicon dioxide in preparation example 2, 0.5kg of antioxidant and 0.5kg of ultraviolet absorbent are uniformly stirred and mixed to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoises, the antioxidant is butylated hydroxytoluene, and the ultraviolet absorbent is phenyl salicylate.
Comparative example
Comparative example 1
Comparative example 1 provides a process for the production of a long-acting drip-inhibiting agent component comprising the steps of:
13kg of polyethylene oxide, 5kg of fatty alcohol polyoxyethylene ether and 3kg of silicone oil are stirred and mixed uniformly to obtain the long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
Comparative example 2
Comparative example 2 provides a process for the production of a long-acting drip-inhibiting agent component comprising the steps of:
10kg of polyethylene oxide, 5kg of fatty alcohol polyoxyethylene ether, 3kg of silicone oil and 3kg of surfactant in preparation example 4 are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
Comparative example 3
Comparative example 3 provides a process for the production of a long-acting drip-inhibiting agent component comprising the steps of:
10kg of polyethylene oxide, 5kg of fatty alcohol polyoxyethylene ether, 3kg of silicone oil and 3kg of modified nano silicon dioxide in preparation example 1 are stirred and mixed uniformly to obtain a long-acting drip agent component, wherein the viscosity of the silicone oil is 500-1000 centipoise.
The performance test is long-lasting, namely, the drip agent components in each example and each comparative example are respectively mixed and fused into polyethylene, the mixed and fused polyethylene is blown into an agricultural film with the thickness of 0.1mm, a sample is obtained, the added mass fraction of the drip agent component is 1.0%, then drip performance test is carried out on each sample according to the drip performance test method provided in the annex A of GB4455-2006, in the test, the test temperature is 60 ℃, the environmental temperature is (23+/-2) DEG C, the initial drip time and the failure time are recorded, and the longer the failure time is, the better the long-acting performance of the drip agent component is.
TABLE 1 results of Performance measurements of the drip agent components
In combination with example 1 and comparative examples 1-3, the anti-drip agent component of example 1 was more time-efficient, and it was found that the addition of the surfactant, modified nanosilica, increased the time-efficient anti-drip agent component when preparing the anti-drip agent component.
In combination with examples 1 to 3, the timeliness of the drip agent component in example 2 is optimal, and it can be seen that the spray coating liquid and the mixture ratio in preparation example 2 and the ratio of glycerin monostearate, sucrose fatty acid ester, pretreated silica and azodiisobutyronitrile are optimal when preparing the modified nano silica, so that the modified nano silica has better performance.
In combination with examples 2, 4 and 5, the timeliness of the drip agent component in example 4 is optimal, and it is seen that the proportion of monoglyceride, 2-methylenesuccinic anhydride, 4-methylbenzenesulfonic acid and 1, 4-benzenediol is optimal in the preparation of the surfactant, so that the performance of the surfactant is better.
In combination with examples 4, 6 and 7, the timeliness of the drip agent component in example 6 was optimal, and it was found that in preparing the drip agent component, the timeliness of the drip agent component obtained exhibited a tendency to rise and then fall with increasing the amount of raw material used.
In combination with examples 6, 8 and 9, it can be seen that the addition of an antioxidant, an ultraviolet absorber to the raw materials in the preparation of the drip formulation component can suitably improve the timeliness of the drip formulation component.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.