阅读说明：本技术 一种低泡型有机硅农用助剂及其合成方法 (Low-foam type organic silicon agricultural additive and synthesis method thereof ) 是由 姜霄云 谭成侠 管仲达 杨森 于 2019-09-27 设计创作，主要内容包括：本发明公开了一种低泡型有机硅农用助剂及其合成方法,所述的低泡型有机硅农用助剂为聚醚酯改性有机硅氧烷,所述聚醚酯改性有机硅氧烷的化学结构式如式(I-1)所示：<Image he="293" wi="700" file="DDA0002218228660000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>式(I-1)中,n＝4～12之间的数值,取代基R为C1～C6的烷基。本发明提出的聚醚酯改性有机硅氧烷无毒害,可以作为农用助剂使用,为一种低泡型农用助剂,泡沫体积约为传统农用助剂的1/4,更适于机械喷洒,提高效率。(The invention discloses a low-foam type organic silicon agricultural auxiliary agent and a synthesis method thereof, wherein the low-foam type organic silicon agricultural auxiliary agent is polyether ester modified organic siloxane, and the chemical structural formula of the polyether ester modified organic siloxane is shown as a formula (I-1): in the formula (I-1), n is a number between 4 and 12, and the substituent R is C1-C6 alkyl. The polyether ester modified organic siloxane provided by the invention is non-toxic, can be used as an agricultural auxiliary agent, is a low-foam agricultural auxiliary agent, has a foam volume which is about 1/4 of that of the traditional agricultural auxiliary agent, is more suitable for mechanical spraying, and improves the efficiency.)

1. The low-foam type organic silicon agricultural additive is characterized in that the low-foam type organic silicon agricultural additive is polyether ester modified organic siloxane, and the chemical structural formula of the polyether ester modified organic siloxane is shown as a formula (I-1):

in the formula (I-1), n is a number between 4 and 12, and the substituent R is C1-C6 alkyl.

2. The low-foam organosilicon agricultural adjuvant according to claim 1, wherein in formula (I-1), n is a number between 5 and 10, and the substituent R is C1-C4 alkyl.

3. The low-foam type organosilicon agricultural adjuvant according to claim 1, characterized in that when the low-foam type organosilicon agricultural adjuvant is dissolved in water to prepare an aqueous solution with a mass concentration of 0.1%, the surface tension is less than or equal to 21.0mN/m by a platinum plate method; 10 microliter of the water solution with the mass concentration of 0.1% of the prepared low-foam organic silicon agricultural additive is transferred and placed on a polystyrene petri dish, and the spreading diameter is tested to be more than or equal to 60mm after the water solution is stood for 30 s.

4. The low-foam type organosilicon agricultural adjuvant according to claim 1, wherein when the low-foam type organosilicon agricultural adjuvant is dissolved in water to prepare an aqueous solution with a mass concentration of 0.1%, 80mL of the aqueous solution with a mass concentration of 0.1% of the prepared low-foam type organosilicon agricultural adjuvant is measured and added into a 250mL measuring cylinder, the measuring cylinder is inverted up and down for 30 times within 1min, the foam volume is less than or equal to 16mL, and the foaming rate is less than or equal to 20%.

5. The method for synthesizing the low-foam type organic silicon agricultural auxiliary agent according to claim 1, which is characterized by comprising the following steps:

1) in the presence of a polymerization inhibitor, carrying out acylation reaction on allyl polyoxyethylene ether shown in a formula (I) and an anhydride compound shown in a formula (II) at the temperature of 100-150 ℃, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain allyl polyoxyethylene ether ester shown in a formula (III);

2) in N₂Carrying out hydrosilylation reaction on the allyl polyoxyethylene ether ester shown in the formula (III) obtained in the step 1) and heptamethyltrisiloxane at the temperature of 90-140 ℃ for 1-3 h under the conditions of atmosphere and catalyst existence, so as to obtain polyether ester modified organosiloxane shown in the formula (I-1); wherein, the reaction formula is as follows:

in the formula (I), the formula (III) and the formula (I-1), n is a number between 5 and 10;

in the formula (II), the formula (III) and the formula (I-1), R is C1-C4 alkyl.

6. The method for synthesizing the low-foam type organosilicon agricultural adjuvant according to claim 5, wherein in the step 1), the polymerization inhibitor is p-hydroxyanisole, hydroquinone or N₂An atmosphere; when the polymerization inhibitor is p-hydroxyanisole, the dosage of the polymerization inhibitor is 0.05-0.2% of the mass of the allyl polyoxyethylene ether shown in the formula (I); when the polymerization inhibitor is hydroquinone, the dosage of the polymerization inhibitor is 0.5-2% of the mass of the allyl polyoxyethylene ether shown in the formula (I).

7. The method for synthesizing the low-foam type organosilicon agricultural adjuvant according to claim 5, wherein in the step 1), the step of post-treating the reaction solution is as follows: and (3) removing most of unreacted anhydride compounds and alkane acid generated by the reaction from the reaction solution through reduced pressure distillation, adding toluene into the reduced pressure distillation concentrate as an azeotropic solvent for removing residual trace anhydride compounds and alkane acid, and continuously performing reduced pressure distillation to remove the solvent according to the same conditions to finally obtain the pure allyl polyoxyethylene ether ester shown in the formula (III).

8. The method for synthesizing the low-foam type organic silicon agricultural auxiliary agent according to claim 7, wherein the amount of the toluene is 1.3-1.6 times of the mass of the acid anhydride compound added during the acylation reaction; the temperature for carrying out reduced pressure distillation is 80-150 ℃, and the pressure for carrying out reduced pressure distillation is-0.099 MPa to-0.095 MPa.

9. The method for synthesizing the low-foam type organosilicon agricultural adjuvant according to claim 5, wherein in step 2), the catalyst is a Spierer catalyst or a Karstedt catalyst.

10. The method for synthesizing the low-foam type organosilicon agricultural adjuvant according to claim 9, characterized in that the catalyst is Karstedt catalyst which is isopropanol solution of platinum-1, 3-divinyltetramethyldisiloxane; the dosage of platinum-1, 3-divinyl tetramethyl disiloxane in the Karstedt catalyst is 0.008-0.016 percent of the mass of the allyl polyoxyethylene ether shown in the formula (I) in the step 1); in the step 2), the temperature for carrying out the hydrosilylation reaction is 90-140 ℃.

Technical Field

The invention belongs to the field of agricultural additives, and particularly relates to a low-foam organic silicon agricultural additive and a synthesis method thereof.

Background

The long-term use of the existing pesticide causes the disease to generate resistance, so that the pesticide consumption is obviously increased, and the environment is seriously damaged. In the application of pesticides, in order to reduce the dosage of pesticides, improve the pesticide effect and reduce the pollution of soil and water, the addition of the high-performance organic silicon agricultural auxiliary agent is an effective, economic and simple method.

The traditional organic silicon agricultural auxiliary agent is generally obtained by hydrosilylation of allyl polyoxyethylene ether and heptamethyltrisiloxane, is an extremely excellent agricultural auxiliary agent due to good spreading performance, excellent wetting performance and low surface tension, and has a large using ratio in pesticides, but the traditional organic silicon agricultural auxiliary agent has the problems of strong foaming and good foam stability, difficult operation and low mechanical spraying efficiency in application.

Disclosure of Invention

Aiming at the technical problems in the prior art, the invention aims to provide a low-foam type organic silicon agricultural auxiliary agent and a synthesis method thereof.

The low-foam type organic silicon agricultural additive is characterized in that the low-foam type organic silicon agricultural additive is polyether ester modified organic siloxane, and the chemical structural formula of the polyether ester modified organic siloxane is shown as a formula (I-1):

in the formula (I-1), n is a number between 4 and 12, and the substituent R is C1-C6 alkyl.

The low-foam organosilicon agricultural adjuvant is characterized in that in the formula (I-1), n is preferably a number between 5 and 10, and a substituent R is C1-C4 alkyl.

The low-foam type organic silicon agricultural additive is characterized in that when the low-foam type organic silicon agricultural additive is dissolved in water to prepare an aqueous solution with the mass concentration of 0.1%, the surface tension of the low-foam type organic silicon agricultural additive is less than or equal to 21.0mN/m by testing with a platinum plate method; 10 microliter of the water solution with the mass concentration of 0.1% of the prepared low-foam organic silicon agricultural additive is transferred and placed on a polystyrene petri dish, and the spreading diameter is measured to be more than or equal to 60mm after the water solution is stood for 30 s.

The low-foam type organic silicon agricultural additive is characterized in that when the low-foam type organic silicon agricultural additive is dissolved in water to prepare an aqueous solution with the mass concentration of 0.1%, 80mL of the aqueous solution with the mass concentration of 0.1% of the prepared low-foam type organic silicon agricultural additive is measured and added into a 250mL measuring cylinder with a plug, the measuring cylinder is inverted up and down for 30 times within 1min, the volume of foam is less than or equal to 16mL, and the foaming rate is less than or equal to 20%.

The synthesis method of the low-foam type organic silicon agricultural additive is characterized by comprising the following steps of:

1) in the presence of a polymerization inhibitor, carrying out acylation reaction on allyl polyoxyethylene ether shown in a formula (I) and an anhydride compound shown in a formula (II) at the temperature of 100-150 ℃, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain allyl polyoxyethylene ether ester shown in a formula (III);

2) in N₂Carrying out hydrosilylation reaction on the allyl polyoxyethylene ether ester shown in the formula (III) obtained in the step 1) and heptamethyltrisiloxane at the temperature of 90-140 ℃ for 1-3 h under the conditions of atmosphere and catalyst existence, so as to obtain polyether ester modified organosiloxane shown in the formula (I-1); wherein, the reaction formula is as follows:

in the formula (I), the formula (III) and the formula (I-1), n is a number between 5 and 10;

in the formula (II), the formula (III) and the formula (I-1), R is C1-C4 alkyl.

The synthesis method of the low-foam type organic silicon agricultural auxiliary agent is characterized in that in the step 1), the polymerization inhibitor is p-hydroxyanisole, hydroquinone or N₂An atmosphere; when the polymerization inhibitor is p-hydroxyanisole, the dosage of the polymerization inhibitor is 0.05-0.2% of the mass of the allyl polyoxyethylene ether shown in the formula (I); when the polymerization inhibitor is hydroquinone, the dosage of the polymerization inhibitor is 0.5-2% of the mass of the allyl polyoxyethylene ether shown in the formula (I).

The synthesis method of the low-foam type organic silicon agricultural additive is characterized in that in the step 1), the step of post-treating the reaction liquid is as follows: and (2) removing most of unreacted anhydride compounds and alkane acids generated by the reaction by reduced pressure distillation, adding toluene serving as an azeotropic solvent into the reduced pressure distillation concentrate to remove residual trace anhydride compounds and alkane acids (the residual trace anhydride compounds and the alkane acids may influence the activity of a catalyst and may influence crops when being used as an agricultural auxiliary agent), and continuously removing the solvent by reduced pressure distillation according to the same conditions to finally obtain the pure allyl polyoxyethylene ether ester shown in the formula (III).

The synthesis method of the low-foam type organic silicon agricultural auxiliary agent is characterized in that the dosage of the toluene is 1.3-1.6 times of the mass of an anhydride compound added in the acylation reaction; the temperature for carrying out reduced pressure distillation is 80-150 ℃, and the pressure for carrying out reduced pressure distillation is-0.099 MPa to-0.095 MPa.

The synthesis method of the low-foam type organic silicon agricultural auxiliary agent is characterized in that in the step 2), the catalyst is a Spierer catalyst (chloroplatinic acid isopropanol solution) or a Karstedt catalyst (platinum-1, 3-divinyl tetramethyl disiloxane isopropanol solution).

The synthesis method of the low-foam type organic silicon agricultural auxiliary agent is characterized in that the catalyst is Karstedt catalyst (isopropanol solution of platinum-1, 3-divinyl tetramethyl disiloxane, the mass fraction of platinum-1, 3-divinyl tetramethyl disiloxane is 8%), and the using amount of the Karstedt catalyst is 0.1-0.2% of the mass of the allyl polyoxyethylene ether shown in the formula (I) in the step 1); in the step 2), the temperature for carrying out the hydrosilylation reaction is 90-140 ℃.

Compared with the prior art, the invention has the following beneficial effects:

1) the application discloses a novel polyether modified organic silicon surfactant (polyether ester modified organic siloxane) as an agricultural auxiliary agent, which has extremely low surface tension when being prepared into an aqueous solution with the mass concentration of 0.1%, the surface tension of the 0.1% aqueous solution is less than or equal to 21.0mN/m when being tested by a platinum plate method, 10 microliter of 0.1% aqueous solution is injected on a polystyrene petri dish by a 25 microliter micro injector, the test spreading diameter after standing for 30s is more than or equal to 60mm, and the agricultural auxiliary agent has better expansibility.

2) The polyether modified organic silicon surfactant provided by the invention is non-toxic and can be used as an agricultural auxiliary agent to reduce the pesticide dosage and improve the pesticide effect, and the pesticide dosage can be saved by more than 30%. It is suitable for spraying herbicide, pesticide, bactericide and plant growth regulator. When the low-foam type organic silicon agricultural additive is prepared into an aqueous solution with the mass concentration of 0.1%, 80mL of the prepared 0.1% aqueous solution is added into a 250mL measuring cylinder with a plug, the volume of the foam is tested to be less than or equal to 16mL within 1min after the solution is inverted up and down for 30 times, the foaming rate is less than or equal to 20%, the low-foam type organic silicon agricultural additive is a low-foam type agricultural additive, the volume of the foam is about 1/4 of the traditional agricultural additive, the low-foam type organic silicon agricultural additive is more suitable for mechanical spraying, and.

Detailed Description

The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.

In the following examples, the molecular structural formula of allyl polyoxyethylene ether is shown in formula (I), and the molecular structural formula of allyl polyoxyethylene ether ester is shown in formula (I-1).

In the following examples, the Karstedt's catalyst was an isopropanol solution of platinum-1, 3-divinyltetramethyldisiloxane, with a mass fraction of platinum-1, 3-divinyltetramethyldisiloxane of 8%.