WO2021063250A1 - Environmentally friendly pesticide emulsifier - Google Patents

Abstract

Disclosed is an environmentally friendly pesticide emulsifier, which is composed of the following components in percentage by mass: 30%-75% of a fatty alcohol polyoxyalkyl ether; 10%-40% of an anionic surfactant; 5%-20% of an antifreeze agent; and 1%-2% of a defoamer, the balance being water. The structural formula of the fatty alcohol polyoxyalkyl ether is R-O-(AO)_a-[(EO)_m-(PO)_n]-H or R-O-[(EO)_m-(PO)_n]-(AO)_a-H, wherein R is an alkyl or alkenyl having 6-18 carbon atoms, A is -CH₂CH₂- or -CH₂CH₂CH₂-CH₂CH₂CH₂CH₂-, (EO)_m-(PO)_n is a polyoxyalkyl chain composed of a -CH₂CH₂O-unit and a -CH₂CH₂CH₂O-unit in a block distribution, alternating distribution or random distribution, a is an integer of 1-10, and m and n are integers of 0-10. The emulsifier of the present invention has an excellent emulsifying effect, does not comprise APEO, is safe and environmentally friendly, and can keep a pesticide aqueous solution stable for a long time when used in the pesticide aqueous solution.

Description

Environment-friendly pesticide emulsifier Technical field

The invention relates to an environmentally friendly pesticide emulsifier.

Background technique

China is the world's major pesticide production and use country. According to statistics, my country's chemical pesticide technical output reached 2.083 million tons in 2018. With the improvement of people's awareness of environmental protection, the requirements for pesticide formulations are getting higher and higher, and pesticide formulations are gradually required to be efficient, safe, and environmentally friendly, and the country has also issued relevant policies and plans. In August 2010, the Ministry of Industry and Information Technology and other four departments jointly issued the "Pesticide Industry Policy", stating that "the country supports efficient, safe, economical, and environmentally friendly pesticides through measures such as scientific and technological support, technological transformation, and economic policy guidance. The development of new products, accelerate the substitution and elimination of high-pollution and high-risk products, and promote the continuous optimization of the variety structure", "vigorously promote the development of agricultural formulations in the direction of water-based, dust-free, controlled release and other high-efficiency and safety... Strict control Use of toxic and harmful solvents and additives". In 2014, the Ministry of Industry and Information Technology issued the "Twelfth Five-Year Development Plan for the Pesticide Industry", which pointed out that "strictly control the use of toxic and harmful solvents and additives containing toluene and xylene, and develop and promote water-based formulations."

Pesticides can be divided into emulsifiable concentrates, suspending agents, liquids, wettable powders and other formulations. Emulsifiable concentrates are currently commonly used pesticide formulations. According to statistics, the number of xylene solvents used in the manufacture of emulsifiable concentrates pesticides in my country is as high as 300,000 to 400,000 tons each year. With the spraying of pesticides, these solvents will first volatilize into the air. Then it will penetrate into food, soil and groundwater, which will not only cause pollution to the ecological environment, but also damage food safety and people's health. Pesticide aqua (a kind of pesticide microemulsion) is safer and more environmentally friendly. It is the direction that the country encourages development. It has developed rapidly in recent years. However, alkylphenol polyoxyethylene ether (APEO) is commonly used as an emulsifier in pesticide aqua. Although APEO has good wetting, penetrating, emulsifying, dispersing, solubilizing effects, but its high toxicity, poor biodegradability, harm to the human body and the ecological environment can not be ignored, some developed countries have banned the use of APEO in many fields.

It can be seen that it is necessary to develop an emulsifier that does not contain APEO, is safe and environmentally friendly, has excellent emulsification effects, and is suitable for pesticide water agents.

Summary of the invention

The purpose of the present invention is to provide an environmentally friendly pesticide emulsifier.

The technical scheme adopted by the present invention is:

An environmentally friendly pesticide emulsifier composed of the following components by mass percentage:

Fatty alcohol polyoxyalkyl ether: 30% to 75%;

Anionic surfactant: 10%～40%;

Antifreeze: 5%-20%;

Defoamer: 1% to 2%;

Water: balance.

Preferably, an environmentally friendly pesticide emulsifier is composed of the following components by mass percentage:

Fatty alcohol polyoxyalkyl ether: 40%～50%;

Anionic surfactant: 10%-20%;

Antifreeze: 5%～15%;

Defoamer: 1% to 2%;

Water: balance.

Preferably, the structural formula of the fatty alcohol polyoxyalkyl ether is:

RO-(AO) _a -[(EO) _m -(PO) _n ]-H or RO-[(EO) _m -(PO) _n ]-(AO) _a -H, where R is the number of carbon atoms 6 ～18 alkyl or alkenyl, A is -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ -, (EO) _m -(PO) _n is -CH ₂ CH ₂ O-units and -CH ₂ CH ₂ CH ₂ O-units are polyoxyalkylene chains composed of block, alternating or random distribution, a is an integer of 1-10, m and n are 0-10 Integer.

Preferably, the anionic surfactant is sodium dodecylbenzene sulfonate, sodium ethoxylated alkyl sulfate, fatty acid methyl ester sulfonate, α-alkenyl sulfonate, sodium secondary alkyl sulfonate At least one of.

Preferably, the antifreeze agent is at least one of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, and sorbitol.

Preferably, the number average molecular weight of the polyethylene glycol is 200-600 g/mol.

Preferably, the defoaming agent is at least one of a silicone defoaming agent and a higher alcohol defoaming agent.

A pesticide water formulation contains the above environmentally friendly pesticide emulsifier.

Preferably, the environmentally-friendly pesticide emulsifier in the pesticide water formulation has a mass percentage of 5% to 15%.

Preferably, the pesticide active ingredient in the pesticide water formulation is at least one of acetamiprid, chlorantraniliprole, thiamethoxam, cyhalofop-butyl, fipronil, atrazine, and mesotrione .

Preferably, the mass percentage of the active ingredient of the pesticide is 1%-15%.

The beneficial effects of the present invention are: the emulsifier of the present invention has excellent emulsification effect, does not contain APEO, is safe and environmentally friendly, and is used in the pesticide water agent to keep the pesticide water agent stable for a long time.

Detailed ways

The present invention will be further explained and illustrated below in conjunction with specific embodiments.

Example 1:

An environmentally friendly pesticide emulsifier, its composition is shown in the following table:

Table 1 Composition table of an environmentally friendly pesticide emulsifier

raw material	Mass percentage (%)
Branched chain type C 12 H 25 -O-(EO) 4 -[(EO) 3 -(PO) 3 ]-H	40
Sodium dodecyl benzene sulfonate	10
Ethylene glycol	10
Silicone defoamer	1
Deionized water	margin

A pesticide water formulation containing the above-mentioned environmentally friendly pesticide emulsifier, and its specific composition is shown in the following table:

Table 2 Composition table of a pesticide water agent

raw material	Mass percentage (%)
Environmentally friendly pesticide emulsifier	10
Acetamiprid	2
Deionized water	margin

Example 2:

An environmentally friendly pesticide emulsifier, its composition is shown in the following table:

Table 3 Composition table of an environmentally friendly pesticide emulsifier

raw material	Mass percentage (%)
Straight chain type C 14 H 29 -O-[(EO) 2 -(PO) 4 ]-(EO) 4 -H	50
Sodium Lauryl Polyvinyl Ether Sulfate	12
Propylene Glycol	10
Silicone defoamer	1
Deionized water	margin

A pesticide water formulation containing the above-mentioned environmentally friendly pesticide emulsifier, and its specific composition is shown in the following table:

Table 4 Composition table of a pesticide water agent

raw material	Mass percentage (%)
Environmentally friendly pesticide emulsifier	7
Chlorantraniliprole	3
Deionized water	margin

Example 3:

An environmentally friendly pesticide emulsifier, its composition is shown in the following table:

Table 5 Composition table of an environmentally friendly pesticide emulsifier

raw material	Mass percentage (%)
Straight chain type C 12 H 25 -O-(EO) 3 -[(EO) 2 -(PO) 3 ]-H	40
α-Alkenyl Sulfonate	12
Propylene Glycol	10
Silicone defoamer	1
Deionized water	margin

A pesticide water formulation containing the above-mentioned environmentally friendly pesticide emulsifier, and its specific composition is shown in the following table:

Table 6 Composition table of a pesticide liquid

raw material	Mass percentage (%)
Environmentally friendly pesticide emulsifier	10
Thiamethoxam	2
Deionized water	margin

Example 4:

An environmentally friendly pesticide emulsifier, its composition is shown in the following table:

Table 7 Composition table of an environmentally friendly pesticide emulsifier

raw material	Mass percentage (%)
Branched chain type C 13 H 27 -O-[(EO) 2 -(PO) 4 ]-(EO) 4 -H	45
Fatty acid methyl ester sulfonate	15
Polyethylene glycol (number average molecular weight 400g/mol)	10
Silicone defoamer	1
Deionized water	margin

A pesticide water formulation containing the above-mentioned environmentally friendly pesticide emulsifier, and its specific composition is shown in the following table:

Table 8 Composition table of a pesticide water agent

raw material	Mass percentage (%)
Environmentally friendly pesticide emulsifier	10
Cyhalofop-butyl	3

Deionized water

margin

Example 5:

An environmentally friendly pesticide emulsifier, its composition is shown in the following table:

Table 9 Composition table of an environmentally friendly pesticide emulsifier

raw material	Mass percentage (%)
Branched chain type C 13 H 27 -O-(EO) 3 -[(EO) 4 -(PO) 4 ]-H	50
Fatty acid methyl ester sulfonate	10
Glycerol	10
Dodecanol	1
Deionized water	margin

A pesticide water formulation containing the above-mentioned environmentally friendly pesticide emulsifier, and its specific composition is shown in the following table:

Table 10 Composition table of a pesticide water agent

raw material	Mass percentage (%)
Environmentally friendly pesticide emulsifier	8
Fipronil	5
Deionized water	margin

Comparative example 1:

A pesticide emulsifier whose composition is shown in the table below:

Table 11 Composition table of a pesticide emulsifier

raw material	Mass percentage (%)
Castor oil polyoxyethylene ether	40
Sorbitan Fatty Acid Ester	20
Glycerol	5
Dodecanol	1
Deionized water	margin

A pesticide water formulation containing the above-mentioned pesticide emulsifier, and its specific composition is shown in the following table:

Table 12 Composition table of a pesticide water agent

raw material

Mass percentage (%)

Pesticide emulsifier	8
Acetamiprid	2
Deionized water	margin

Comparative example 2:

A pesticide emulsifier whose composition is shown in the table below:

Table 13: Composition table of a pesticide emulsifier

raw material	Mass percentage (%)
Polyoxyethylene laureth ether	50
Linear deca alcohol polyoxyethylene ether	30
Propylene Glycol	5
Silicone defoamer	1
Deionized water	margin

A pesticide water formulation containing the above-mentioned pesticide emulsifier, and its specific composition is shown in the following table:

Table 14 Composition table of a pesticide water agent

raw material	Mass percentage (%)
Pesticide emulsifier	10
Chlorantraniliprole	3
Deionized water	margin

Comparative example 3:

A pesticide emulsifier whose composition is shown in the table below:

Table 15 Composition table of a pesticide emulsifier

raw material	Mass percentage (%)
Sodium Laureth Sulfonate	40
Sodium decyl alcohol polyoxyethylene ether carboxylate	20
Propylene Glycol	5
Silicone defoamer	2
Deionized water	margin

A pesticide water formulation containing the above-mentioned pesticide emulsifier, and its specific composition is shown in the following table:

Table 16 Composition table of a pesticide water agent

raw material	Mass percentage (%)
Pesticide emulsifier	8
Thiamethoxam	2
Deionized water	margin

Comparative example 4:

A pesticide liquid, its composition is shown in the following table:

Table 17 Composition table of a pesticide water agent

raw material	Mass percentage (%)
Branched chain type C 13 H 27 -O-(EO) 3 -[(EO) 4 -(PO) 4 ]-H	8
Fipronil	5
Deionized water	margin

Comparative Example 5:

A pesticide liquid, its composition is shown in the following table:

Table 18 Composition table of a pesticide water agent

raw material	Mass percentage (%)
Fatty acid methyl ester sulfonate	8
Fipronil	5
Deionized water	margin

Note:

In Examples 1 to 5 and Comparative Example 4, EO is a -CH ₂ CH ₂ O- unit, and PO is a -CH ₂ CH ₂ CH ₂ O- unit.

Test case:

1) The pesticide aqueous formulations of Examples 1 to 5 and Comparative Examples 1 to 5 were tested for dispersibility and stability. The test results are shown in the following table:

Table 19 Test results of the dispersibility and stability of the pesticide aqueous preparations of Examples 1 to 5 and Comparative Examples 1 to 5

test group	Dispersion	stability	Low temperature precipitation rate (%)	Heat storage precipitation rate (%)
Example 1	First level	No floating milk, no precipitation	0	3.6
Example 2	First level	No floating milk, no precipitation	0	4.9
Example 3	First level	No floating milk, no precipitation	0	3.8

Example 4	Level 2	No floating milk, no precipitation	0	4.2
Example 5	Level 2	No floating milk, no precipitation	0	5.1
Comparative example 1	Level 3	Very small amount of floating milk, no precipitation	2.2	twenty one
Comparative example 2	Level 3	A small amount of floating milk, no precipitation	1.2	26
Comparative example 3	Level 4	A small amount of floating milk, a small amount of precipitation	9.3	33
Comparative example 4	Level 3	A small amount of floating milk, no precipitation	1.4	20
Comparative example 5	Level 4	A small amount of floating milk, the precipitation is obvious	3.6	32

Note:

Dispersion test method: Pour 1mL of pesticide water into a 250mL beaker, then dilute 200 times with standard hard water with a concentration of 342mg/L, and stir continuously with a glass rod, then put the beaker in a constant temperature water bath at 30±2℃ Let stand for 1h under the conditions of, and grade according to the following standards:

Level I: Automatically uniformly dispersed in cloud and mist, no visible oil droplets, clear and transparent samples;

Level Two: Automatically uniformly dispersed in cloud and mist, without visible oil droplets, and the sample is clear and translucent;

Level 3: Automatically dispersed in cloud and mist, without visible oil droplets, and the sample is clear and white;

Level 4: Partially dispersed automatically, the emulsified particles are coarse, and the sample is white;

Level 5: It will not automatically disperse, it will be in the form of oil droplets in water, it can be emulsified after shaking, and it will layer quickly when placed.

Stability test method: refer to GB/T 1603-2001 for testing. Add 99.5mL of standard hard water into a 250mL beaker. Use a pipette to suck up 0.5mL of the pesticide liquid, and slowly add it to the hard water under constant stirring to make a 100mL emulsion. After adding the emulsion, continue stirring at a speed of 2～3r/s for 30s, immediately transfer the emulsion to a clean and dry 100mL graduated cylinder, and place the graduated cylinder in a constant temperature water bath, and let it stand at 30±2℃ Take it out for 1 hour and observe the separation of the emulsion. If there is no slick oil, oil sinking or precipitation in the graduated cylinder, the emulsion stability is judged to be qualified.

Low temperature precipitation rate test method: refer to GB/T 19137-2003 Determination of Low Temperature Stability of Pesticides for testing. Pipette 100mL of pesticide aqueous solution into a centrifuge tube, cool it to 0±2℃ in a refrigerator, keep the centrifuge tube and its contents at 0±2℃ for 1h, and stir once every 15min, 15s each time, check And record whether solid or oily matter precipitated. Put the centrifuge tube back into the refrigerator, keep it at 0±2℃ for 7 days, after 7 days, take out the centrifuge tube, let it stand at room temperature for 3 hours, centrifuge for 15 minutes (the relative centrifugal force at the top of the tube is 500-600g, g is the acceleration of gravity), Record the volume of the educt at the bottom of the tube (accurate to 0.05 mL), and calculate the precipitation rate.

Thermal storage precipitation rate test method: refer to GB/T 19136-2003 Pesticide Thermal Storage Stability Test Method for testing. Use a syringe to inject about 30 mL of pesticide water into a clean ampoule, place the ampoule in an ice-salt bath for refrigeration, seal with a high-temperature flame, and cool to room temperature to weigh. Place the sealed ampoule in a metal container, then place the metal container in a thermostat at 54±2°C for 14 days, take it out, wipe the outside of the ampoule and weigh it, and calculate the precipitation for the sample with no change in mass rate.

It can be seen from Table 19:

1) The environmentally friendly pesticide emulsifiers of Examples 1 to 5 have good emulsification and dispersibility, and have a good emulsification effect when diluted with water, and a clear pesticide liquid can be obtained;

2) The pesticide aqueous formulations of Examples 1 to 5 have good emulsion stability and will not be stratified during normal transportation, while the pesticide aqueous formulations of Comparative Examples 1 to 5 have been stratified under the test conditions;

3) The pesticide aqueous formulations of Examples 1 to 5 have stable performance under low temperature conditions and can still maintain a stable and uniform solution system, while the pesticide aqueous formulations of Comparative Examples 1 to 5 have different degrees of substance precipitation;

4) Under high temperature conditions, none of the pesticide aqueous formulations had precipitation stratification, but the precipitation rate of the pesticide aqueous formulations of Examples 1 to 5 was much lower than that of the pesticide aqueous formulations of Comparative Examples 1 to 5, indicating that their high temperature stability was better ；

5) Fatty alcohol polyoxyalkyl ethers and anionic surfactants are both essential components and have excellent synergistic effects. The overall effect of the two components is better than that of a single component.

2) The emulsion particle size and particle size distribution test were carried out on the pesticide aqueous formulations of Examples 1 to 5 and Comparative Examples 1 to 5, and the test results are shown in the following table:

Table 20 Test results of particle size and particle size distribution of the emulsions of the pesticide aqueous formulations of Examples 1 to 5 and Comparative Examples 1 to 5

test group	Emulsion particle size (nm)	Particle size distribution
Example 1	58	0.055
Example 2	55	0.098
Example 3	60	0.075
Example 4	85	0.068
Example 5	80	0.096
Comparative example 1	110	0.135
Comparative example 2	120	0.165
Comparative example 3	280	0.203
Comparative example 4	130	0.180
Comparative example 5	430	0.290

Note:

The particle size and particle size distribution of the emulsion are tested using a dynamic particle size tester.

The smaller the particle size of the emulsion, the less likely it is to settle, the better the dispersion effect, and the smaller the particle size is also conducive to the effective ingredients penetrating the epidermis of plants or insects, and better exerting the efficacy.

The smaller the particle size distribution value, the narrower the particle size distribution. When PDI≤0.1, the distribution is uniform, and when PDI≥0.2, the distribution is uneven.

It can be seen from Table 20:

1) The particle size of the emulsions of the pesticide aqueous agents of Examples 1 to 5 are all less than 100nm, and the particle size distribution value is less than 0.1, while the particle size of the emulsions of Comparative Examples 1 to 5 are all greater than 100nm, and the particle size distribution value is greater than 0.1, indicating The pesticide water preparations of Examples 1 to 5 are more stable, are not easy to separate and settle, and have uniform particle size distribution;

2) Fatty alcohol polyoxyalkyl ethers and anionic surfactants are both essential components and have excellent synergistic effects. The overall effect of the two components is better than that of a single component.

The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, etc. made without departing from the spirit and principle of the present invention Simplified, all should be equivalent replacement methods, and they are all included in the protection scope of the present invention.

Claims (10)

1. An environmentally friendly pesticide emulsifier, which is characterized in that it is composed of the following components by mass percentage:

   Fatty alcohol polyoxyalkyl ether: 30% to 75%;

   Anionic surfactant: 10%～40%;

   Antifreeze: 5%-20%;

   Defoamer: 1% to 2%;

   Water: balance;

   The structural formula of the fatty alcohol polyoxyalkyl ether is:

   RO-(AO) _a -[(EO) _m -(PO) _n ]-H or RO-[(EO) _m -(PO) _n ]-(AO) _a -H, where R is the number of carbon atoms 6 ～18 alkyl or alkenyl, A is -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ -, (EO) _m -(PO) _n is -CH ₂ CH ₂ O-units and -CH ₂ CH ₂ CH ₂ O-units are polyoxyalkylene chains composed of block, alternating or random distribution, a is an integer of 1-10, m and n are 0-10 Integer.
2. The environmentally friendly pesticide emulsifier according to claim 1, characterized in that it is composed of the following components by mass percentage:

   Fatty alcohol polyoxyalkyl ether: 40%～50%;

   Anionic surfactant: 10%-20%;

   Antifreeze: 5%～15%;

   Defoamer: 1% to 2%;

   Water: balance.
3. The environmentally friendly pesticide emulsifier according to claim 1 or 2, wherein the anionic surfactant is sodium dodecylbenzene sulfonate, sodium ethoxylated alkyl sulfate, and fatty acid methyl ester sulfonate , At least one of α-alkenyl sulfonate and sodium secondary alkyl sulfonate.
4. The environmentally friendly pesticide emulsifier according to claim 1 or 2, wherein the antifreeze agent is at least one of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, and sorbitol.
5. The environmentally friendly pesticide emulsifier according to claim 4, wherein the number average molecular weight of the polyethylene glycol is 200-600 g/mol.
6. The environmentally friendly pesticide emulsifier according to claim 1 or 2, wherein the defoamer is at least one of a silicone defoamer and a higher alcohol defoamer.
7. A pesticide water preparation, characterized in that it contains the environmentally friendly pesticide emulsifier according to any one of claims 1 to 6.
8. The pesticide water preparation according to claim 7, wherein the environmentally friendly pesticide emulsifier has a mass percentage content of 5% to 15%.
9. The pesticide water preparation according to claim 7 or 8, characterized in that: the active ingredient of the pesticide is acetamiprid, chlorantraniliprole, thiamethoxam, cyhalofop-butyl, fipronil, atrazine, nitrosulfuron At least one of oxalin.
10. The pesticide water preparation according to claim 9, characterized in that the mass percentage of the pesticide active ingredient is 1%-15%.