Organosilicon dispersant for oil suspending agent and synthesis method thereof

Abstract

The invention discloses an organic silicon dispersing agent for an oil suspending agent and a synthesis method of the organic silicon dispersing agent, and relates to the field of organic silicon. Organic silicon groups in molecules prepared by the method can well wet the surface of a pesticide raw medicine, meanwhile, macromolecules can effectively wrap and anchor the pesticide raw medicine, and a traditional surfactant part in the macromolecules can play a role in emulsifying an oil phase.

Description

Technical Field

[0001] This invention relates to the field of organosilicon, and more specifically to an organosilicon dispersant for oil suspension and its synthesis method. Background Technology

[0002] Pesticide technicals that are easily hydrolyzed in water are generally formulated as oil suspensions. The oil phase solvent used in oil suspensions is difficult to wet the pesticide technical, thus requiring prolonged milling to reduce the particle size. Simultaneously, the oil phase needs to address the issue of emulsification in water during use, necessitating the addition of emulsifiers. However, emulsifiers are often small molecules with insufficient coating properties for the pesticide technical. Summary of the Invention

[0003] The purpose of this invention is to at least solve one of the technical problems existing in the prior art, and to provide an organosilicon dispersant for oil suspension and its synthesis method.

[0004] The technical solution of the present invention is as follows: A method for synthesizing an organosilicon dispersant for oil suspensions, characterized by comprising the following steps: S1: Methyl butyne diacetate and heptamethyltrisiloxane are heated to 70-90℃, a catalyst is added and reacted, and the mixture is distilled under reduced pressure to obtain intermediate 1. S2: Mix intermediate 1 with hydrochloric acid aqueous solution, heat to 55-65℃ to react, distill under reduced pressure until no distillate remains, heat to 90℃ and continue distilling under reduced pressure until no distillate remains, to obtain intermediate 2; S3: Intermediate 2 and monomethyl-terminated polyoxyethylene ether are mixed, heated to 50°C for reaction, and after being cooled to room temperature, xylene is added. After washing with water, the organic phase is distilled under reduced pressure to remove the solvent xylene, thus obtaining intermediate 3. S4: Mix intermediate 3 and thionyl chloride, distill under reduced pressure until no fraction remains, then add a nonionic surfactant to react while distilling under reduced pressure; after cooling to room temperature, add xylene, wash with water, and then distill the organic phase under reduced pressure to remove the solvent xylene, thus obtaining intermediate 4. S5: After heating intermediate 4, ethanol, and azobisisobutyronitrile to 70°C, slowly add an ethanol solution of intermediate 4 dropwise, controlling the temperature not to exceed 90°C. After the addition is complete, react and remove the solvent ethanol by vacuum distillation to obtain the product.

[0005] Specifically, the reaction process is as follows: ; ; ; ; R is a straight-chain or branched alkyl or alkylphenol with 8-18 carbon atoms; Traditional polyoxyethylene ether nonionic surfactants.

[0006] Preferably, in step S1, the catalyst is a platinum acid catalyst, and the reaction time is 4-6 hours.

[0007] Preferably, in step S2, the concentration of the hydrochloric acid aqueous solution is 10 wt%.

[0008] Preferably, in step S4, the nonionic surfactant is octanol polyoxyethylene ether and / or tridecyl alcohol polyoxyethylene ether.

[0009] Preferably, in step S5, 10-14 parts by weight of intermediate 4, 25-30 parts by weight of ethanol, and 0.1-0.15 parts by weight of azobisisobutyronitrile are heated to 70°C, and then 150-200 parts by weight of an ethanol solution containing 40-50 parts by weight of intermediate 4 is slowly added dropwise, while controlling the temperature not to exceed 90°C. After the addition is complete, the reaction is carried out for 0.5-1.5 hours, and the solvent ethanol is removed by vacuum distillation to obtain the product.

[0010] The present invention also discloses an organosilicon dispersant for oil suspensions, which is prepared by any of the synthesis methods described above.

[0011] The present invention also discloses an oil suspension agent comprising the above-mentioned organosilicon dispersant.

[0012] The beneficial effects of this invention are: this invention combines traditional surfactants with organosilicon surfactants to form a polymeric dispersant emulsifier containing organosilicon. The organosilicon groups in the molecule can effectively wet the surface of the pesticide active ingredient, while the polymer can effectively encapsulate and anchor the pesticide active ingredient, and the traditional surfactant portion in the polymer can emulsify the oil phase. Detailed Implementation

[0013] The embodiments of the present invention are described in detail below. These embodiments are exemplary and are only used to explain the present invention, and should not be construed as limiting the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0014] Synthesis of Intermediate 1: In a four-necked flask, 28.4 g of methyl butyryne diacetate and 53.5 g of heptamethyltrisiloxane (H-307) were added. After heating to 80 °C, 5 ppm (calculated as H2PtCl6) of chloroplatinic acid catalyst was added, and the reaction was carried out for 5 h. Unreacted heptamethyltrisiloxane was removed by vacuum distillation at 120 °C to obtain 72.9 g of product Intermediate 1.

[0015] Synthesis of Intermediate 2: In a four-necked flask, 72.9 g of Intermediate 1 and 20 g of 10% hydrochloric acid aqueous solution were added. The mixture was stirred and heated to 60°C. After reacting for 5 hours, the mixture was distilled under reduced pressure until no distillate was obtained. The temperature was then raised to 90°C and distilled under reduced pressure until no distillate was obtained. 63.5 g of Intermediate 2 was obtained.

[0016] Synthesis of intermediate 3: In a four-necked flask, 63.5 g of intermediate 2 and 144.0 g of monomethyl-terminated polyoxyethylene ether (MPEG600) (n=13) were stirred and heated to 50°C for 5 hours. After cooling to room temperature, 500 g of xylene was added, and the mixture was washed twice with water. The organic phase was then distilled under reduced pressure to remove the solvent xylene, yielding 183.1 g of intermediate 3.

[0017] Example 1 In a four-necked flask, 46.1 g of intermediate 3 and 7.0 g of thionyl chloride were added, and the mixture was stirred at room temperature for 2 hours. The mixture was then distilled under reduced pressure until no fraction remained. Next, 24.1 g of octanol polyoxyethylene ether (m=7) was added, and the mixture was distilled under reduced pressure for 3 hours while reacting. After cooling to room temperature, 300 g of xylene was added, and the mixture was washed twice with water. The organic phase was then distilled under reduced pressure to remove the solvent xylene, yielding 67.0 g of intermediate 4-1.

[0018] In a three-necked flask, add 12.0 g of intermediate 4-1, 28.0 g of ethanol, and 0.12 g of azobisisobutyronitrile (AIBN). After heating to 70°C, slowly add 48.0 g of an ethanol solution (160.0 g) of intermediate 4-1 dropwise, controlling the temperature to not exceed 90°C. After the addition is complete, react for 1 hour. Remove the solvent ethanol by vacuum distillation to obtain 60.0 g of product, which is product 1.

[0019] Example 2 In a four-necked flask, 46.1 g of intermediate 3 and 7.0 g of thionyl chloride were added, and the mixture was stirred at room temperature for 2 hours. The mixture was then distilled under reduced pressure until no fraction remained. Next, 35.2 g of isomeric tridecyl alcohol polyoxyethylene ether (m=7) was added, and the mixture was distilled under reduced pressure for 3 hours while reacting. After cooling to room temperature, 300 g of xylene was added, and the mixture was washed twice with water. The organic phase was then distilled under reduced pressure to remove the solvent xylene, yielding 77.8 g of intermediate 4-2.

[0020] In a three-necked flask, add 15.0 g of intermediate 4-1, 45.0 g of ethanol, and 0.15 g of azobisisobutyronitrile (AIBN). After heating to 70°C, slowly add 48.0 g of an ethanol solution (200.0 g) of intermediate 4-2, controlling the temperature to not exceed 90°C. After the addition is complete, react for 1 hour. Remove the solvent ethanol by vacuum distillation to obtain 75.0 g of product, which is product 2.

[0021] Application Example 1 Weigh 2.55g penflusulfonamide, 9.00g finished product 1, 2.00g organic bentonite, and 86.45g methyl oleate into a sand mill cup. Add an appropriate amount of zirconium oxide sand mill beads. After sand milling for 120 minutes, filter to remove the sand mill beads to obtain 98g penflusulfonamide (2.5%) oil suspension.

[0022] Application Example 2 Weigh 2.55g penflusulfonamide, 7.00g finished product 2, 2.00g organic bentonite, and 88.45g methyl oleate into a sand mill cup. Add an appropriate amount of zirconium oxide sand mill beads. After sand milling for 100 minutes, filter to remove the sand mill beads to obtain 98g penflusulfonamide (2.5%) oil suspension.

[0023] Application Example 3 Weigh 5.10g of nicosulfuron, 20.41g of atrazine, 10.00g of product 1, 1.50g of organic bentonite, and 62.99g of methyl oleate into a sand mill cup. Add an appropriate amount of zirconium oxide sand mill beads, and sand mill for 90 minutes. After filtering to remove the sand mill beads, obtain 97g of nicosulfuron-atrazine (5%+20%) oil suspension.

[0024] Application Example 4 Weigh 20.30g of oxazolidinyl, 9.00g of product 2, 1.30g of organic bentonite, and 69.40g of mineral oil into a sand mill cup. Add an appropriate amount of zirconium oxide sand mill beads. After sand milling for 80 minutes, filter to remove the sand mill beads to obtain 97g of oxazolidinyl (20%) oil suspension.

[0025] Comparative Example 1 Weigh 20.30g of oxazolidinyl, 9.00g of product 2, 1.30g of organic bentonite, and 69.40g of mineral oil into a sand mill cup. Add an appropriate amount of zirconium oxide sand mill beads. After sand milling for 80 minutes, filter to remove the sand mill beads to obtain 97g of oxazolidinyl (20%) oil suspension.

[0026] Comparative Example 2 Weigh 2.55g penflusulfonamide, 7.00g isotridecyl polyoxyethylene ether (m=7), 2.00g organic bentonite, and 88.45g methyl oleate into a sand mill cup. Add an appropriate amount of zirconium oxide sand mill beads. After sand milling for 100 minutes, filter to remove the sand mill beads to obtain 98g penflusulfonamide (2.5%) oil suspension.

[0027] Comparative Example 3 Weigh 5.10g of nicosulfuron, 20.41g of atrazine, 10.00g of octanol polyoxyethylene ether (m=7), 1.50g of organobentonite, and 62.99g of methyl oleate into a sand milling cup. Add an appropriate amount of zirconium oxide sand milling beads, and sand mill for 90 minutes. After filtering to remove the sand milling beads, obtain 97g of nicosulfuron-atrazine (5%+20%) oil suspension.

[0028] Comparative Example 4 Weigh 20.30g of oxazolidinyl, 9.00g of isotridecyl alcohol polyoxyethylene ether (m=7), 1.30g of organobentonite, and 69.40g of mineral oil into a sand milling cup. Add an appropriate amount of zirconium oxide sand milling beads, and sand mill for 80 minutes. After filtering to remove the sand milling beads, obtain 97g of oxazolidinyl (20%) oil suspension.

[0029] The particle size range (one drop of sample was added to a test tube containing 10 ml of deionized water and shaken well. The sample was then poured into a laser particle size analyzer, ultrasonically stirred for 2 seconds, and the average value D90 was measured) and thermal stability (tested by storing the sample at 54℃±2℃ for 2 weeks according to the "Liquid Preparations" test method in GB / T 19136-2003) were evaluated. The test results are shown in Table 1.

[0030] Table 1 Performance test results of application examples and comparative examples

[0031] As shown in Table 1, when Examples 1 and 2 were applied to oil suspensions (Application Examples 1-4), there was no change in appearance before and after heat storage, while precipitation occurred in the comparative examples. This indicates that the organosilicon dispersant of the present invention has wetting, dispersing and emulsifying effects as an oil suspension for pesticides, and has good stability.

[0032] The embodiments described above are merely preferred embodiments of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various other corresponding changes and modifications based on the technical solutions and concepts described above, and all such changes and modifications should fall within the protection scope of the claims of the present invention.

Claims

1. A method for synthesizing an organosilicon dispersant for oil suspensions, characterized in that, Includes the following steps: S1: Methyl butyne diacetate and heptamethyltrisiloxane are heated to 70-90℃, a catalyst is added and reacted, and the mixture is distilled under reduced pressure to obtain intermediate 1. S2: Mix intermediate 1 with hydrochloric acid aqueous solution, heat to 55-65℃ to react, distill under reduced pressure until no distillate remains, heat to 90℃ and continue distilling under reduced pressure until no distillate remains, to obtain intermediate 2; S3: Intermediate 2 and monomethyl-terminated polyoxyethylene ether are mixed, heated to 50°C for reaction, and after being cooled to room temperature, xylene is added. After washing with water, the organic phase is distilled under reduced pressure to remove the solvent xylene, thus obtaining intermediate 3. S4: Mix intermediate 3 and thionyl chloride, distill under reduced pressure until no fraction remains, then add a nonionic surfactant to react while distilling under reduced pressure; after cooling to room temperature, add xylene, wash with water, and then distill the organic phase under reduced pressure to remove the solvent xylene, thus obtaining intermediate 4. S5: After heating intermediate 4, ethanol, and azobisisobutyronitrile to 70°C, slowly add an ethanol solution of intermediate 4 dropwise, controlling the temperature not to exceed 90°C. After the addition is complete, react and remove the solvent ethanol by vacuum distillation to obtain the product.

2. The method for synthesizing an organosilicon dispersant for oil suspension according to claim 1, characterized in that, In step S1, the catalyst is a platinum acid catalyst, and the reaction time is 4-6 hours.

3. The method for synthesizing an organosilicon dispersant for oil suspension according to claim 1, characterized in that, In step S2, the concentration of the hydrochloric acid aqueous solution is 10 wt%.

4. The method for synthesizing an organosilicon dispersant for oil suspension according to claim 1, characterized in that, In step S4, the nonionic surfactant is octanol polyoxyethylene ether and / or tridecyl alcohol polyoxyethylene ether.

5. The method for synthesizing an organosilicon dispersant for oil suspension according to claim 1, characterized in that, In step S5, 10-14 parts by weight of intermediate 4, 25-30 parts by weight of ethanol, and 0.1-0.15 parts by weight of azobisisobutyronitrile are heated to 70°C, and then 150-200 parts by weight of an ethanol solution containing 40-50 parts by weight of intermediate 4 are slowly added dropwise, while controlling the temperature not to exceed 90°C. After the addition is complete, the reaction is carried out for 0.5-1.5 hours. The solvent ethanol is removed by vacuum distillation to obtain the product.

6. An organosilicon dispersant for oil suspensions, characterized in that, It is prepared by any of the synthesis methods described in claims 1-5.

7. An oil suspension agent, characterized in that, Includes the organosilicon dispersant as described in claim 6.

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