阅读说明：本技术 一种稳定的啶虫脒水悬浮制剂及提高啶虫脒水悬浮制剂稳定性的方法 (Stable acetamiprid water suspension preparation and method for improving stability of acetamiprid water suspension preparation ) 是由 罗昌炎 詹姆斯.T.布里斯托 于 2019-05-06 设计创作，主要内容包括：本发明涉及一种稳定的啶虫脒水悬浮制剂及提高啶虫脒水悬浮制剂稳定性的方法,通过在含有啶虫脒活性物的水悬浮剂中添加植物油,从而抑制了啶虫脒悬浮颗粒在储存过程中粒径增长的风险,有效提高了含啶虫脒的水悬浮剂的储存稳定性。(The invention relates to a stable acetamiprid water suspension preparation and a method for improving the stability of the acetamiprid water suspension preparation.)

1. The stable acetamiprid water suspension preparation is characterized by comprising vegetable oil, wherein the weight ratio of the acetamiprid active matter to the vegetable oil is (5-40) - (1-10).

2. The acetamiprid aqueous suspension formulation of claim 1, which consists of:

dispersed acetamiprid active, from 5 to 40 wt% relative to the total composition;

b vegetable oil, which is 1 to 10% by weight relative to the total composition;

c, a dispersant, which is 1 to 8% by weight relative to the total composition;

d, an emulsifier, which is 1 to 8% by weight relative to the total composition;

e, optionally one or more agriculturally acceptable further additives, from 0% to 15% by weight, relative to the total composition;

water, from 40 to 90% by weight relative to the total composition;

optionally other agriculturally active, from 0 to 20% by weight, relative to the total composition.

3. The acetamiprid aqueous suspension formulation according to claim 2, which consists of the following components:

dispersed acetamiprid active at 10 to 30 wt% relative to the total composition;

b vegetable oil, from 2 to 8% by weight relative to the total composition;

c, a dispersant, which is 2 to 5% by weight relative to the total composition;

d, an emulsifier, which is 1 to 5% by weight relative to the total composition;

e, optionally one or more agriculturally acceptable further additives, from 1% to 10% by weight, relative to the total composition;

water, from 50 to 80% by weight relative to the total composition;

optionally other agriculturally active, from 0 to 20% by weight, relative to the total composition.

4. An aqueous suspension formulation of acetamiprid according to any one of claims 1 to 3, wherein the vegetable oil is selected from any one or a mixture of at least two of corn oil, soybean oil, castor oil, palm oil, rapeseed oil, peanut oil, linseed oil or pine nut based vegetable oils.

5. An aqueous acetamiprid suspension formulation according to any one of claims 2 to 4, wherein the agriculturally acceptable further additives are selected from any one or a mixture of at least two of antifoam, antifreeze, thickener, pH adjuster, pigment, antioxidant or preservative.

6. An acetamiprid aqueous suspension formulation according to any one of claims 2 to 5, wherein the other agricultural active is selected from any one or a mixture of at least two of abamectin, emamectin benzoate, ivermectin, imidacloprid or thiamethoxam, preferably abamectin.

7. The acetamiprid aqueous suspension formulation according to any one of claims 1 to 6, which consists of the following components:

dispersed acetamiprid active at 10 to 30 wt% relative to the total composition;

b vegetable oil, from 2 to 8% by weight relative to the total composition;

c, a dispersant, which is 2 to 5% by weight relative to the total composition;

d, an emulsifier, which is 1 to 5% by weight relative to the total composition;

one or more other agrochemically acceptable additives in an amount of from 1 to 10 wt.% relative to the total composition;

water, from 50 to 80% by weight relative to the total composition;

dispersed abamectin agricultural active, from 0% to 15% by weight with respect to the total composition.

8. A method for improving the stability of an acetamiprid aqueous suspension preparation, which is characterized by comprising the step of adding vegetable oil into the acetamiprid aqueous suspension preparation.

9. The method of claim 8, wherein the acetamiprid aqueous suspension comprises the acetamiprid active substance and the vegetable oil in a weight ratio of (5-40) to (1-10).

Technical Field

The invention relates to the field of pesticides, in particular to an acetamiprid water suspension preparation, and particularly relates to a stable acetamiprid water suspension preparation and a method for improving the stability of the acetamiprid water suspension preparation.

Background

Acetamiprid belongs to chloronicotinyl compounds, has the English common name of acetamiprid and the chemical name of N- (N-cyano-ethylimino) -N-methyl-2-chloropyridine-5-methylamine. Acetamiprid is a novel pesticide. The appearance is white crystal, the melting point is 101.0-103.3 ℃, and the vapor pressure is>1.33×10^-6Pa (25 ℃). The water solubility at 25 deg.C is 4200mg/L, and the extract can be dissolved in acetone, methanol, ethanol, dichloromethane, chloroform, acetonitrile, tetrahydrofuranPyran, and the like. It is stable in water at pH 7, and at pH 9, it is gradually hydrolyzed at 45 deg.C and is stable in sunlight. At present, the main preparation products are missible oil, aqueous emulsion, wettable powder and water dispersible granules.

The water suspension preparation is one of the accepted environment-friendly formulations in the pesticide industry, and the appearance of the formulation opens wide development prospect for the production and application of a plurality of pesticides which are neither hydrophilic nor lipophilic. The suspending agent is a new formulation developed in the 70 s of the 20 th century, is relatively short in the development history of pesticide preparations, develops very rapidly and is continuously improved at home and abroad in recent decades, partially replaces wettable powder and missible oil, and gradually becomes an excellent formulation for replacing powder preparations. However, the pesticide used in the preparation of the aqueous suspension is limited in that the water solubility of the active ingredient of the pesticide is 100mg/L or less, preferably insoluble. Otherwise, the austenite curing phenomenon, namely the crystal growth phenomenon, is easy to occur in the storage process of the preparation. For the pesticide with the solubility in water being slightly more than 100mg/L, the stable aqueous suspension can be prepared by adjusting the auxiliary agent, but the processing difficulty is higher. However, the solubility of the acetamiprid in water is 4200mg/L which is far more than 100mg/L, so the processing of the acetamiprid into a stable water suspension agent is very difficult.

CN106719621A discloses a surfactant composition for an acetamiprid aqueous suspension agent and a preparation method thereof, which mainly describes that the surfactant composition provided by the scheme can produce an acceptable 20% acetamiprid aqueous suspension agent, the surfactant composition mainly comprises a block copolymer of ethylene oxide and propylene oxide, xanthan gum, magnesium aluminum silicate, ethylene glycol and water, but the surfactant can not obtain the acetamiprid aqueous suspension agent with high concentration, and the obtained acetamiprid aqueous suspension agent has larger particle size growth rate of acetamiprid suspended particles and is not beneficial to long-term storage.

CN105052993A discloses that adding 5% -20% of vegetable oil into an aqueous pesticide suspension containing fipronil, glyphosate and dicamba as active ingredients is synergistic, wherein the vegetable oil is added as a synergist of the suspension, and the stability of the aqueous suspension is not improved.

In conclusion, the acetamiprid aqueous suspension preparation prepared at present still has the problem that the acetamiprid solubility is too high, so that the acetamiprid suspended particles are subjected to austenite ripening in the process of normal-temperature storage or thermal storage in an aqueous solution, so that the particle size growth rate is too high, and the stability of the acetamiprid aqueous suspension preparation is influenced. Therefore, it is still of great importance to develop an aqueous suspension formulation of acetamiprid which can maintain a low rate of particle size growth during storage.

Disclosure of Invention

Aiming at the problems that the acetamiprid with high water solubility is easy to generate an austenite curing phenomenon when being processed into a water suspension agent and the crystal growth is larger, the invention aims to provide a stable acetamiprid water suspension preparation.

In order to achieve the purpose, the invention adopts the following technical scheme:

a stable acetamiprid aqueous suspension preparation contains vegetable oil, and the weight ratio of acetamiprid active matter to vegetable oil is (5-40) - (1-10).

The invention selects one or more vegetable oils, so that the acetamiprid aqueous suspension can effectively control the problem of crystal grain size increase caused by austenite ripening of acetamiprid in the storage process, greatly inhibit the grain size increase of high water-solubility acetamiprid suspended particles, improve the stability of the preparation and improve the insecticidal effect of acetamiprid.

In the present invention, the inventors have surprisingly found that the addition of vegetable oil can effectively inhibit the grain size growth caused by the austenite ripening of the acetamiprid suspended particles, which is totally against the common knowledge of researchers' surprise and the prior art on the use of vegetable oil in aqueous suspending agents.

In the invention, the weight ratio of the acetamiprid to the vegetable oil is (5-40) - (1-10), such as 1:2, 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 10:5, 20:7, 30:10, 40:10 and the like.

In the present invention, the vegetable oil is selected from any one or a mixture of at least two of corn oil, soybean oil, castor oil, palm oil, rapeseed oil, peanut oil, linseed oil, pine nut-based vegetable oil, sunflower seed oil, coconut oil, cottonseed oil, or sesame oil, wherein typical but non-limiting mixtures are, for example, corn oil and soybean oil; castor oil and palm oil; rapeseed oil, peanut oil and coconut oil.

Preferably, the acetamiprid aqueous suspension preparation consists of the following components:

dispersed acetamiprid active, from 5 to 40 wt% relative to the total composition;

b vegetable oil, which is 1 to 10% by weight relative to the total composition;

c, a dispersant, which is 1 to 8% by weight relative to the total composition;

d, an emulsifier, which is 1 to 8% by weight relative to the total composition;

e, optionally one or more agriculturally acceptable further additives, from 0% to 15% by weight, relative to the total composition;

water, from 40 to 90% by weight relative to the total composition;

optionally other agriculturally active, from 0 to 20% by weight, relative to the total composition.

In the present invention, the acetamiprid active weight percentage of component a in the aqueous suspension is 5-40%, such as 5%, 6%, 10%, 15%, 20.4%, 23.6%, 28%, 30%, 33.9%, 37%, 39% or 40%, preferably 10-30%.

In the present invention, the vegetable oil weight percentage of the B component in the aqueous suspension is 1-10%, such as 1%, 1.2%, 2%, 2.3%, 2.8%, 4%, 5%, 7%, 8%, 8.8%, 9.3%, 9.8% or 10%, preferably 2-8%.

In the present invention, the dispersant weight percentage of the C component in the aqueous suspension is 1 to 8%, for example 1%, 1.5%, 2%, 3%, 4%, 5%, 5.5%, 6%, 7.2%, 7.5%, 7.9% or 8%, preferably 2 to 5%.

In the present invention, the emulsifier content of component D in the aqueous suspension concentrate is 1-8% by weight, such as 1%, 1.3%, 2%, 2.3%, 4%, 5%, 5.5%, 6.1%, 7%, 7.4%, 7.8% or 8%, preferably 1-5%.

In the present invention, the optional one or more agriculturally acceptable further additives of the E component of the aqueous suspension concentrate are present in an amount of 0 to 10% by weight, for example 0%, 1%, 2%, 2.5%, 3%, 4%, 5%, 5.4%, 6%, 7%, 8%, 8.6%, 9% or 10%, preferably 1 to 5%.

In the present invention, the water content of the F component in the aqueous suspension concentrate is 40-90% by weight, for example 40%, 43%, 45%, 50%, 55%, 60%, 66%, 70%, 75, 78%, 80%, 85%, 88% or 90%, preferably 50-80%.

In the present invention, the aqueous suspension also contains an optional agricultural active as component G in an amount of 0 to 20% by weight, for example 0%, 1%, 3%, 5%, 7%, 8%, 9%, 10%, 12%, 13%, 15%, 16%, 17%, 18%, 19% or 20%, preferably 0 to 15%.

Further preferably, the acetamiprid aqueous suspension preparation comprises the following components:

dispersed acetamiprid active at 10 to 30 wt% relative to the total composition;

b vegetable oil, from 2 to 8% by weight relative to the total composition;

c, a dispersant, which is 2 to 5% by weight relative to the total composition;

d, an emulsifier, which is 1 to 5% by weight relative to the total composition;

e, optionally one or more agriculturally acceptable further additives, from 1% to 10% by weight, relative to the total composition;

water, from 50 to 80% by weight relative to the total composition;

optionally other agriculturally active, from 0 to 20% by weight, relative to the total composition.

The dispersant described in the present invention is selected from any one or a mixture of at least two of lignosulfonate, naphthalene sulfonate formaldehyde polycondensate, triphenylethylene ethoxylated sulfate, triphenylethylene ethoxylated phosphate, polycarboxylate or methacrylate copolymer, wherein a typical but non-limiting mixture is: a mixture of lignosulfonate and naphthalene sulfonate formaldehyde polycondensates; a mixture of a triphenylethylene ethoxylated phosphate, a polycarboxylate, and a methacrylate copolymer; a mixture of naphthalene sulfonate formaldehyde polycondensate, triphenylethylene ethoxylated sulfate and triphenylethylene ethoxylated phosphate.

The emulsifier described in the present invention is selected from the group consisting of reactants of alkyl phenols with ethylene oxide and/or propylene oxide, ethoxylated nonyl phenols, ethylene oxide propylene oxide block copolymers, castor oil ethoxylates, alkyl calcium salts, calcium alkyl benzene sulfonates, sorbitan derivatives or sorbitan fatty acid esters, or mixtures of any one or at least two thereof, wherein typical but non-limiting mixtures are: a mixture of ethoxylated nonylphenol and ethylene oxide propylene oxide block copolymers, a mixture of castor oil ethoxylates, calcium alkyl salts, calcium alkyl benzene sulfonates and sorbitan derivatives.

The optional one or more agriculturally acceptable other additives described in the present invention may be defoamers, antifreeze agents, thickeners, preservatives, antioxidants, colorants, inert materials, and the like.

In the present invention, suitable antifoaming agents include all substances commonly used for this purpose in agrochemical compositions, preferably the antifoaming agent is a silicone antifoaming agent, preferably a siloxane antifoaming agent.

Suitable antifreeze agents in the context of the present invention include all substances which are customarily used for this purpose in agrochemical compositions, preferably propylene glycol and/or ethylene glycol.

Suitable thickeners in the context of the present invention include all substances commonly used for this purpose in agrochemical compositions, preferably xanthan gum.

In the present invention, suitable preservatives include all substances commonly used for this purpose in agrochemical compositions, preferably selected from the Proxel series and/or the Nipacide series of preservatives.

Suitable antioxidants in the context of the present invention include all substances which are customarily used for this purpose in agrochemical compositions, preferably the antioxidant is 2, 6-di-tert-butyl-4-methylphenol.

In the present invention, suitable colorants include all substances commonly used for this purpose in agrochemical compositions, preferably the colorant is any one or a combination of at least two of titanium dioxide, zinc oxide, blue Pigment or Pigment Red BBN (i.e. fast Red BBN).

In the present invention, suitable inert materials include all materials commonly used for this purpose in agrochemical compositions, preferably the inert filler material is any one or a combination of at least two of urea, silicate, sulphate or oxide.

In the present invention, other agriculturally active compounds, preferably insecticides, may also be included.

Suitable insecticides include Abamectin (Abamectin), Spinosad (Spinosad), Spinetoram (Spinetoram), Imidacloprid (Imidacloprid), clothianidin (clothianidin), thiacloprid (thiamcloprid), thiamethoxam (thiamethoxam), nitenpyram (nitenpyram), dinotefuran (dinotefuran), lufenuron (lufenuron), bifenthrin (bifenthrin), cypermethrin (cyperimethrin), deltamethrin (deltamethrin), permethrin (permethrin), fenpropathrin (fenpropathrin), cyfluthrin (cyfluthrin), cyhalothrin (laumba-cyhalothrin), methiocarb (methcarb), thiodicarb (thiodicarb), methiocarb (halocarb), ametryn (halocarb), teflufenozide (diflufenuron), teflufenoxaprop-uron (Diflubenzuron), tebufenozide (flufenozide), teflufenoxaprop-ethyl (Diflubenzuron), teflufenozide (Diflubenzuron (flufenozide), teflufenozide (Diflubenzuron (fenozide), tebufenon (fenozide), teflufenozide (fenozide), tebufenozide), teflufenozide (fenozide), teflufenoxaprop-ethyl (fenozide), texaprop-ethyl (fenoxaprop-ethyl (fenozide), texaprop-ethyl (teflufenozide), texaprop-ethyl (fenozide), texaprop-ethyl (teflufenozide), texaprop-ethyl (texabenuron (texaprop, Tebufenozide (Tebufenozide), furaffenozide (Fufenozide), Flonicamid (floramid), Diafenthiuron (Diafenthiuron), dimethyl ether (Amitraz), lambda-cyfluthrin (Beta-cyfluthrin), Tefluthrin (Tefluthrin), Etoxazole (Etoxazole), Spirotetramat (Spirotetramat), biphenylcarbonitrile (Bifenazate), Methoxyfenozide (Methoxyfenozide), Pyridaphenthion (pyriphnthentothion), and monosultap (Thiosultap-monosodium).

Preferred insecticides are Abamectin (Abamectin), Emamectin benzoate (Emamectin benzoate), Ivermectin (Ivermectin), Imidacloprid (Imidacloprid), Thiamethoxam (Thiamethoxam). More preferably Abamectin (Abamectin).

When the abamectin is the preferred other agricultural active substance, the acetamiprid water suspension preparation consists of the following components:

dispersed acetamiprid active at 10 to 30 wt% relative to the total composition;

b vegetable oil, from 2 to 8% by weight relative to the total composition;

c, a dispersant, which is 2 to 5% by weight relative to the total composition;

d, an emulsifier, which is 1 to 5% by weight relative to the total composition;

one or more other agrochemically acceptable additives in an amount of from 1 to 10 wt.% relative to the total composition;

water, from 50 to 80% by weight relative to the total composition;

dispersed abamectin agricultural active, from 0% to 15% by weight with respect to the total composition.

On the other hand, the invention also provides a preparation method of the acetamiprid-containing water suspension preparation, which comprises the following steps: and stirring and mixing the component A, the component B, the component C, the component D, the component F, the optional component E and the optional component G, and grinding to obtain the acetamiprid-containing water suspension agent.

Preferably, the grinding is performed at 10-50 ℃, e.g., 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃, preferably 15-40 ℃.

Preferably, the milling is to a particle size D90 ≦ 10 μm of the solid particles of the oil-based concentrate, such as 0.5 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm, preferably D90 ≦ 6 μm.

In the invention, the solid particle D90 of the acetamiprid-containing water suspension preparation is less than 10 microns, the particle size change is small under the conditions of normal-temperature storage and/or heat storage, the growth is relatively slow, and the stability is kept for a long time. The preparation method has the advantages of low formula cost, simple process, low requirement on equipment and high processing efficiency.

The invention also provides a method for improving the stability of the acetamiprid aqueous suspension preparation, which comprises the step of adding vegetable oil into the acetamiprid aqueous suspension preparation.

The invention unexpectedly uses the vegetable oil to inhibit the problem that the crystal growth is caused by long-term storage and/or heat storage of the water suspending agent prepared from the acetamiprid with high water solubility due to austenite ripening, overcomes the problem that the water suspending agent cannot be prepared from the high water-soluble active substances in the traditional sense, and provides a method for preparing the water suspending agent from the active substances with high water solubility.

In the method, in the acetamiprid water suspension preparation, the weight ratio of the acetamiprid active matter to the vegetable oil is (5-40) - (1-10), such as 1:2, 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 10:5, 20:7, 30:10, 40:10 and the like.

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

(1) according to the invention, the plant oil is added into the acetamiprid water suspension preparation, so that the acetamiprid water suspension preparation can effectively control the problem of crystal particle size increase caused by austenite curing of acetamiprid in the storage process, the particle size increase of high-water-solubility acetamiprid suspension particles is greatly inhibited, the stability of the preparation is improved, and the insecticidal effect of the acetamiprid is improved; the problem that the water suspending agent cannot be prepared from the high water-solubility active substance in the traditional sense is also solved, and a method for preparing the water suspending agent from the active substance with high water solubility is provided; specifically, the acetamiprid water suspension preparation containing vegetable oil has a grain size growth rate of less than 6 percent when stored at 54 ℃ for 7 days and a grain size growth rate of less than 11 percent when stored for 14 days, and the grain size growth rate is obviously reduced compared with the acetamiprid water suspension preparation without vegetable oil;

(2) compared with the acetamiprid water suspension preparation without vegetable oil, the stable acetamiprid water suspension preparation prepared by the invention has obviously improved insecticidal effect.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.