Environment-friendly emulsifier suitable for methyl oleate and preparation method of environment-friendly emulsifier

Abstract

The invention discloses an environment-friendly emulsifier suitable for methyl oleate and a preparation method thereof, and the emulsifier comprises the following components in percentage by mass: 10-25% of triphenylethyl phenol polyoxyethylene ether phosphate, 5-40% of dodecylbenzene sulfonate, 10-50% of castor oil polyoxyethylene polyoxypropylene ether, 5-20% of isodecanol polyoxyethylene, 5-20% of sodium dodecyl benzene sulfonate, 5-20% of sodium dodecyl benzene sulfonate, 5-20% of sodium dodecyl benzene sulfonate and the balance of water. And complementing with methyl oleate. The emulsifier disclosed by the invention has excellent emulsifying performance on plant-derived methyl oleate, does not contain alkylphenol polyoxyethylene ether compounds harmful to the ecological environment, and is particularly suitable for being used as an environment-friendly emulsifying auxiliary agent of various pesticide preparations taking plant-derived methyl oleate as a solvent.

Description

Technical Field

[0001] The invention belongs to the technical field of agricultural emulsifiers, and particularly relates to an environmentally friendly emulsifier which is suitable for plant-based methyl oleate and does not contain alkylphenol polyoxyethylene ether compounds harmful to the ecological environment, and a preparation method thereof. Background Art

[0002] Alkylphenol polyoxyethylene ether (APEO) is the abbreviation of alkylphenol polyoxyethylene ether compounds. It is a polyoxyethylene nonionic surfactant and the main representative of the currently widely used nonionic surfactants. It has good wetting, penetration, emulsification, dispersion, solubilization and washing effects, and is widely used in the processing and manufacturing of detergents, personal care products, textiles, papermaking, petroleum, metallurgy, pesticides, pharmaceuticals, printing, synthetic rubber, synthetic resins, plastics and even food industry products. The most important use is washing products and textile auxiliaries.

[0003] APEO biodegrades slowly, and after degradation, it produces APEO and alkylphenol (AP) with less ethoxyl (EO), and produces biodegradable metabolites nonylphenol (NP) and octylphenol (OP). Its metabolites NP and OP can also cause harm to the human body. NP, OP, NPEO and OPEO are all environmental hormone chemicals. After invading the human body, they have effects similar to estrogen, the so-called "female effect" and reproductive distortion, and have become the natural enemy of all living things, including humans.

[0004] Great attention and importance are paid to the use and limitation of nonylphenol and nonylphenol polyether both at home and abroad.

[0005] Germany already banned the use of APEOs in detergents as early as 1998. EU regulations have prohibited the use of NPEOs in formulations at concentrations above 0.1% since January 2005. These compounds often end up in wastewater, causing problems for the environment.

[0006] In July 2012, Germany proposed to include nonylphenol in the list of substances of very high concern under the REACH regulation. In December of the same year, nonylphenol appeared in the eighth batch of the list of substances of very high concern and was defined as potentially harmful to the environment. The restrictions are as follows: When the concentration of nonylphenol and nonylphenol polyoxyethylene ether is greater than or equal to 0.1%, they shall not be placed on the market or used as ingredients of substances or mixtures for the following purposes: industrial and institutional cleaning agents, household cleaning, treatment of textiles and leather products, agricultural emulsifiers, metal processing, pulp and paper formulations, cosmetics, other personal care products, pesticides or antibiotic formulations.

[0007] In 2016, the EU amended the REACH regulation, and from 2021, the use of nonylphenol polyoxyethylene ether in textile products is banned.

[0008] In my country, the use of nonylphenol to produce nonylphenol polyoxyethylene ether is prohibited from March 1, 2023. In combination with my country's current management regulations, three control measures are taken: first, the use of nonylphenol as an adjuvant in the production of pesticide products is prohibited; second, the use of nonylphenol to produce nonylphenol polyoxyethylene ether is prohibited; third, nonylphenol is prohibited from being used as a cosmetic component.

[0009] Nonylphenol polyoxyethylene ether is a major alkylphenol polyoxyethylene ether compound, accounting for 80-85% of it. Nonylphenol polyoxyethylene ether has excellent emulsification, wettability and permeability, especially in the emulsification of vegetable oils and their methyl ester derivatives. It is also one of the most widely used agricultural surfactants.

[0010] In the future, how to avoid APEO in the production of agricultural adjuvants and pesticides, how to replace APEO and meet the needs of production and use, especially the development of emulsified substitutes for vegetable oils and their methyl ester derivatives, has become the most concerned and urgent problem in the industry. Summary of the invention

[0011] The purpose of the present invention is to provide an environmentally friendly emulsifier suitable for methyl oleate, which does not contain alkylphenol polyoxyethylene ether compounds such as nonylphenol / octylphenol that are harmful to the ecological environment.

[0012] Another object of the present invention is to provide a method for preparing the above-mentioned environmentally friendly emulsifier suitable for methyl oleate.

[0013] The object of the present invention is achieved in the following ways:

[0014] An environmentally friendly emulsifier suitable for methyl oleate, comprising the following components in percentage by weight:

[0015]

[0016] The above-mentioned environmentally friendly emulsifier suitable for methyl oleate contains the following components in percentage by mass:

[0017]

[0018] Preferably, the dodecylbenzene sulfonate is calcium dodecylbenzene sulfonate.

[0019] The above-mentioned preparation method applicable to the environmentally friendly emulsifier of methyl oleate comprises the following steps:

[0020] Step 1: preheating dodecylbenzene sulfonate, triphenyl ethyl phenol polyoxyethylene ether phosphate, castor oil polyoxyethylene polyoxypropylene ether and isomeric decanol polyoxyethylene for 3-5 hours respectively at a temperature of 40-50°C; preheating to improve their fluidity so as to produce the extraction material;

[0021] Step 2: Add the preheated dodecylbenzene sulfonate, triphenyl phenol polyoxyethylene ether phosphate, castor oil polyoxyethylene polyoxypropylene ether and isomeric decanol polyoxyethylene into the reaction kettle in sequence, then add methyl oleate, turn on the stirrer, continue stirring evenly, and cool naturally to obtain.

[0022] Preferably, the temperature in the reactor is room temperature. The emulsifier is suitable for dispersible oil suspensions and emulsifiable concentrates.

[0023] In the present invention, calcium dodecylbenzene sulfonate and castor oil polyoxyethylene ether polyoxypropylene ether are used as emulsifiers to synergistically play an excellent emulsifying effect on the plant-based methyl oleate solvent, which is conducive to its emulsification in water; triphenyl ethyl phenol polyoxyethylene ether phosphate plays the role of an emulsifying dispersant, assists the emulsifier in dispersing and emulsifying in water, and improves the stability of the emulsion; isomeric decanol polyoxyethylene is used as a wetting agent in the present invention to promote the full wetting of the surface of solid particles, thereby facilitating the production of pesticide dispersible oil suspensions and emulsifiable concentrates.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows: the emulsifier of the present invention has excellent emulsifying properties for plant-derived methyl oleate, does not contain alkylphenol polyoxyethylene ether compounds that are harmful to the ecological environment, and is suitable for use as an environmentally friendly emulsifying aid for various pesticide preparations using plant-derived methyl oleate as a solvent, such as 4% nicosulfuron dispersible oil suspension and 15% cyhalofop-butyl emulsifiable concentrate. DETAILED DESCRIPTION

[0025] The present invention is further described in detail below in conjunction with the following examples, but the embodiments of the present invention are not limited thereto. In the following examples, triphenyl ethyl phenol polyoxyethylene ether phosphate (Agricultural milk 600P, 85%, a commercial product of Nanjing Keyi New Materials Co., Ltd.), dodecylbenzene sulfonate (emulsifier 500#, 70%, a commercial product of Nanjing Keyi New Materials Co., Ltd.), castor oil polyoxyethylene polyoxypropylene ether (98%, a commercial product of Nanjing Keyi New Materials Co., Ltd.), isomeric decanol polyoxyethylene (1008, 99%, BASF), methyl oleate (1107, purchased from Jiangsu Fengbei Biotechnology Co., Ltd.)

[0026] Example 1

[0027] The mass percentage of each substance in the emulsifier is: 10% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 30% of calcium dodecylbenzene sulfonate, 40% of castor oil polyoxyethylene polyoxypropylene ether, 10% of isomeric decanol polyoxyethylene, and methyl oleate as a supplement.

[0028] Preparation method: According to the formula of this embodiment, all materials except methyl oleate are preheated at 40-50°C for 3-5h, and then the materials triphenyl ethyl phenol polyoxyethylene ether phosphate, dodecylbenzene sulfonate, castor oil polyoxyethylene polyoxypropylene ether, and isomeric decanol polyoxyethylene are added to the reaction kettle in sequence, and methyl oleate is supplemented to 100%. The stirrer is turned on, and after stirring evenly, it is cooled to room temperature to obtain the finished emulsifier.

[0029] Example 2

[0030] The mass percentage of each substance in the emulsifier is: 20% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 10% of calcium dodecylbenzene sulfonate, 30% of castor oil polyoxyethylene polyoxypropylene ether, 15% of isomeric decanol polyoxyethylene, and methyl oleate as a supplement

[0031] Preparation method: Same as Example 1.

[0032] Example 3

[0033] The mass percentage of each substance in the emulsifier is: 15% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 30% of calcium dodecylbenzene sulfonate, 35% of castor oil polyoxyethylene polyoxypropylene ether, 10% of isomeric decanol polyoxyethylene, and methyl oleate as a supplement.

[0034] Preparation method: Same as Example 1.

[0035] Example 4

[0036] The mass percentage of each substance in the emulsifier is: 10% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 30% of calcium dodecylbenzene sulfonate, 30% of castor oil polyoxyethylene polyoxypropylene ether, 10% of isomeric decanol polyoxyethylene, and methyl oleate is used as a supplement.

[0037] Preparation method: Same as Example 1

[0038] Example 5

[0039] The mass percentage of each substance in the emulsifier is: 15% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 20% of calcium dodecylbenzene sulfonate, 40% of castor oil polyoxyethylene polyoxypropylene ether, 10% of isomeric decanol polyoxyethylene, and methyl oleate as a supplement.

[0040] Preparation method: Same as Example 1

[0041] Example 6

[0042] The mass percentage of each substance in the emulsifier is: 10% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 25% of calcium dodecylbenzene sulfonate, 35% of castor oil polyoxyethylene polyoxypropylene ether, 15% of isomeric decanol polyoxyethylene, and methyl oleate as a supplement.

[0043] Preparation method: Same as Example 1

[0044] Example 7

[0045] The mass percentage of each substance in the emulsifier is: 10% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 30% of calcium dodecylbenzene sulfonate, 25% of castor oil polyoxyethylene polyoxypropylene ether, 10% of isomeric decanol polyoxyethylene, and methyl oleate as a supplement.

[0046] Preparation method: Same as Example 1

[0047] Example 8

[0048] The mass percentage of each substance in the emulsifier is: 20% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 30% of calcium dodecylbenzene sulfonate, 20% of castor oil polyoxyethylene polyoxypropylene ether, 15% of isomeric decanol polyoxyethylene, and methyl oleate makes up the rest.

[0049] Preparation method: Same as Example 1.

[0050] Comparative Example 1

[0051] The mass percentages of the various substances in the comparative emulsifiers are as follows: 5% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 30% of dodecylbenzene sulfonic acid, 40% of castor oil polyoxyethylene polyoxypropylene ether, 10% of isomeric decanol polyoxyethylene, and methyl oleate as a supplement.

[0052] The remaining components and preparation steps are the same as those in Example 1, except that the amount of triphenyl phenol polyoxyethylene ether phosphate used is less.

[0053] Comparative Example 2

[0054] The mass percentages of the various substances in the comparative emulsifiers are as follows: triphenyl ethyl phenol polyoxyethylene ether phosphate 15%, dodecylbenzenesulfonic acid triethanolamine salt (content 70%) 30%, castor oil polyoxyethylene polyoxypropylene ether 35%, isomeric decanol polyoxyethylene 10%, and methyl oleate as a supplement.

[0055] The preparation steps are the same as those of Example 1, except that 70% of calcium dodecylbenzenesulfonate is replaced by 70% of triethanolamine dodecylbenzenesulfonate.

[0056] Comparative Example 3

[0057] The mass percentages of the various substances in the comparative emulsifiers are as follows: 15% of triphenyl ethyl phenol polyoxyethylene ether phosphate, 30% of dodecylbenzene sulfonic acid, 35% of castor oil polyoxyethylene polyoxypropylene ether, 10% of isomeric decanol polyoxyethylene, and methyl oleate as a supplement.

[0058] The remaining preparation steps are the same as those in Example 1, except that all materials are not preheated. The isomeric decanol polyoxyethylene ether has a stratification phenomenon, and the other materials have high viscosity, which causes production inconvenience, and the materials are not mixed evenly, so a homogeneous emulsifier product cannot be obtained.

[0059] Example 9

[0060] Application as an emulsifier for pesticide dispersible oil suspension: 4% Nicosulfuron dispersible oil suspension.

[0061] Application formulation (mass percentage): nicosulfuron 4%, emulsifier (Example 1-4) 15%, organic bentonite (thickener) 2%, methyl oleate to 100%. Preparation method: weigh all materials according to the formula, mix, disperse evenly, and sand grind for 1-2 hours to obtain the finished preparation.

[0062] Control preparation: 4% Nicosulfuron dispersible oil suspension (in which the emulsifier is mainly nonylphenol polyoxyethylene ether)

[0063] The control preparation formula (mass percentage): nicosulfuron 4%, emulsifier (nonylphenol polyoxyethylene ether 60%, calcium dodecylbenzene sulfonate 20%, methyl oleate 20%) 18%, organic bentonite (thickener) 2%, methyl oleate is added. Preparation method: weigh all materials according to the formula, mix them, disperse them evenly, and grind them in a sand mill for 1-2 hours to obtain the control preparation product.

[0064] Comparative preparation 1: Homemade 4% Nicosulfuron dispersible oil suspension (emulsifier is Comparative Example 1)

[0065] Comparative preparation 1 formula (mass percentage): nicosulfuron 4%, emulsifier (comparative example 1) 15%, organic bentonite (thickener) 2%, methyl oleate supplement. Preparation method: weigh all materials according to the formula, mix, disperse evenly, and sand grind with a sand mill for 1-2 hours to obtain the finished preparation.

[0066] Comparative preparation 2: Homemade 4% Nicosulfuron dispersible oil suspension (emulsifier is Comparative Example 2)

[0067] Comparative preparation 2 formula (mass percentage): nicosulfuron 4%, emulsifier (comparative example 2) 15%, organic bentonite (thickener) 2%, methyl oleate supplement. Preparation method: weigh all materials according to the formula, mix, disperse evenly, and sand grind with a sand mill for 1-2 hours to obtain the finished preparation.

[0068] Table 1 Physical and chemical stability of 4% Nicosulfuron dispersible oil suspension

[0069]

[0070] The 4% nicosulfuron dispersible oil suspension prepared by the emulsifier of the present invention has good stability and is better than the control agent in terms of suspension rate. In addition, the preparations prepared by comparative examples 1 and 2 have low suspension rates and unqualified heat storage stability, and are unqualified preparation products.

[0071] Example 10

[0072] Application as an emulsifier for pesticide emulsifiable concentrates: 15% Quizalofop-Ph-ethyl EC.

[0073] The formulation of the application preparation (mass percentage): 15% of Quizalofop-Ph-ethyl, 10% of the emulsifier (Example 5-8), and methyl oleate to 100%.

[0074] Preparation method: according to the formula, weighed quizalofop-p-ethyl and methyl oleate are mixed and stirred, and after quizalofop-p-ethyl is fully dissolved in methyl oleate, an emulsifier is added and stirred evenly to obtain a finished preparation.

[0075] Control preparation: Homemade 15% Quizalofop-ethyl EC (commercially available)

[0076] Comparative preparation 3: Homemade 15% Quizalofop-ethyl EC (emulsifier is the same as that in Comparative Example 1)

[0077] Comparative preparation 3 formula (mass percentage): 15% of quizalofop-p-ethyl, 10% of emulsifier (comparative example 1), and methyl oleate as a supplement. Preparation method: According to the formula, weighed quizalofop-p-ethyl and methyl oleate are mixed and stirred, and after quizalofop-p-ethyl is fully dissolved in methyl oleate, the emulsifier is added and stirred evenly to obtain the finished preparation.

[0078] Comparative preparation 4: Homemade 15% Quizalofop-ethyl EC (emulsifier is Comparative Example 2)

[0079] Comparative preparation 4 formula (mass percentage): 15% of quizalofop-p-ethyl, 10% of emulsifier (Comparative Example 2), and methyl oleate as supplement. Preparation method: According to the formula, weighed quizalofop-p-ethyl and methyl oleate are mixed and stirred, and after quizalofop-p-ethyl is fully dissolved in methyl oleate, the emulsifier is added and stirred evenly to obtain the finished preparation.

[0080] Table 2 Physical and chemical stability of 15% Quizalofop-ethyl EC

[0081]

[0082] The 15% quizalofop-p-ethyl emulsifiable concentrate prepared by using the emulsifier of the present invention has excellent stability. In addition, the emulsification, heat storage stability and low temperature stability of the preparations prepared by using Comparative Examples 1 and 2 are all unqualified.

[0083] Comparative Example of Drug Efficacy

[0084] (1) The 4% nicosulfuron application preparation prepared in Example 9 (emulsifier is Example 1-4) was used as the test agent, and the commercially available 4% nicosulfuron dispersible oil suspension was used as the control agent to conduct a drug efficacy experiment.

[0085] Dosage of the drug: 50ml / mu

[0086] Target of prevention and control: Weeds such as crabgrass, foxtail grass, dayflower and ramie in corn fields.

[0087] Crop: Corn (1-4 leaves)

[0088] The specific results of drug efficacy are shown in the following table.

[0089] Table 3 Comparison of the efficacy of 4% Nicosulfuron dispersible oil suspension (15 days after application)

[0090] Pharmacy Crataegus Setaria Commelina Ramie The preparation containing Example 1 90％ 89％ 88％ 92％ The preparation containing Example 2 91％ 88％ 90％ 90％ The preparation containing Example 3 89％ 90％ 89％ 91％ The preparation containing Example 4 90％ 91％ 88％ 89％ Control preparation 82％ 80％ 79％ 82％

[0091] (2) Comparative experiment on the efficacy of 15% quizalofop-p-ethyl EC

[0092] The 15% quizalofop-ethyl emulsifiable concentrate application preparation (emulsifier is Example 5-8) prepared in Example 10 was used as the test agent, and the commercially available 15% quizalofop-ethyl emulsifiable concentrate was used as the control agent for the efficacy experiment.

[0093] Dosage of drug: 20ml / mu

[0094] Targets of prevention and control: Gramineae weeds such as crabgrass, foxtail grass, barnyard grass and goosegrass in soybean fields.

[0095] Crop: Soybean (1-4 leaves)

[0096] The specific results of drug efficacy are shown in the following table.

[0097] Table 4 Comparison of the efficacy of 15% Quizalofop-ethyl EC (15 days after drug administration)

[0098] Pharmacy Crataegus Setaria Goosegrass Barnyard grass The preparation containing Example 5 87％ 89％ 87％ 85％ The preparation containing Example 6 90％ 86％ 88％ 86％ The preparation containing Example 7 89％ 88％ 89％ 87％ The preparation containing Example 8 86％ 87％ 87％ 89％ Control preparation 80％ 74％ 70％ 72％

[0099] The efficacy data in Table 3 and Table 4 show that the medicaments prepared by the present invention are significantly better than the control medicaments in terms of use effect and have excellent synergistic effects.

[0100] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An environmentally friendly emulsifier suitable for methyl oleate, characterized in that Contains the following components in percentage by mass:

2. The environmentally friendly emulsifier suitable for methyl oleate according to claim 1, characterized in that Contains the following components in percentage by mass:

3. The environmentally friendly emulsifier suitable for methyl oleate according to claim 1 or 2, characterized in that The dodecylbenzene sulfonate is calcium dodecylbenzene sulfonate.

4. A method for preparing an environmentally friendly emulsifier for methyl oleate according to claim 1 or 2, characterized in that The method comprises the following steps: Step 1: preheating dodecylbenzene sulfonate, triphenyl ethyl phenol polyoxyethylene ether phosphate, castor oil polyoxyethylene polyoxypropylene ether and isomeric decanol polyoxyethylene for 3-5 hours respectively at a temperature of 40-50°C; Step 2: Add the preheated dodecylbenzene sulfonate, triphenyl phenol polyoxyethylene ether phosphate, castor oil polyoxyethylene polyoxypropylene ether and isomeric decanol polyoxyethylene into the reaction kettle in sequence, then add methyl oleate, turn on the stirrer, continue stirring evenly, and cool naturally to obtain.

5. The method for preparing an environmentally friendly emulsifier for methyl oleate according to claim 4, characterized in that The temperature in the reactor is room temperature.

6. The method for preparing an environmentally friendly emulsifier for methyl oleate according to claim 4, characterized in that The emulsifier is suitable for dispersible oil suspensions and emulsifiable concentrates.

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