Dispensatory mixture, agricultural pesticide composition and method of increasing the dissolution rate of the block - copolymer of ethylene oxide and propylene oxide

 

(57) Abstract:

The inventive mixtures of block copolymers of ethylene oxide/propylene oxide (EO/PO) with anionic polymers and surface-active substances (surfactants) can be used as a dispersant in agriculture, particularly in pesticide compositions. The mixture contains, by weight. % include block copolymers EO/PO, containing at least 70% EO units, 85-92, polyacrylates 5-12, at least one line of Las 0.1 to 5, when the total content of all components is 100 wt.%. The invention provides an increased rate of dissolution of the block copolymer of EO/water (less than 6.5 minutes). 3 S. and 12 C.p. f-crystals, 2 tab.

The invention relates to surfactant mixtures of block copolymers of ethylene oxide/propylene oxide (EO/PO) with anionic polymers and surface-active substances (surfactants). In comparison with the actual EO/PO-block copolymers such mixtures have a high dissolution rate and can be used as a dispersant in agriculture, particularly in pesticide compositions.

Block copolymers of ethylene oxide and propylene oxide are well known nonionic surface-aktivni functions and physical properties. Their exceptional versatility has led to a widespread demand for these in different markets and in different areas of technology. Many of these surface-active substances are, among other such valuable qualities as panagsama/protivovspenivayushchie, cleansing properties, the ability to impart solubility, foaming, emulsifying and wetting properties.

EO/PO-block copolymer surfactants are also extremely effective as a dispersant in aqueous medium, in particular in pesticide compositions. Dispersion is a system containing solid particles in a liquid continuous phase. Thus, pesticide dispersion includes particles activitiesthese substances dispersed in a liquid medium. Therefore, a good surfactant or dispersant inhibits the natural tendency of solid particles to stick together among themselves or to recombination. Thus, dispersers are designed to assist in the resolution of these two problems, as flocculation and the formation of hard agglomerates.

The dissolution rate EO/PO-block copolymers largely determines their suitability for use as disaste surfactants to stabilize the solid material in the liquid system. Unfortunately, the rate of dissolution of many EO/PO-block copolymers may be quite low, in many cases preventing, thus, the possibility of their use as a dispersant.

Especially effective nonionic surface-active dispersing agents one of the groups have the following formula:

< / BR>
where x, y and x' represent such numbers that the block copolymer is more than 50% is hydrophilic, often more than 70% hydrophilic, and molecular mass (MW) its hydrophobic part is 950-4000. The molecular mass of each of these compounds exceeds 1000; market firm BASF Corporation supplied under the trademark PLURONIC. It should be noted EO/PO-block copolymer represented by the above formula, the molecular mass of which is equal to 8400. This compound is marketed under the trademark PLURONICF68.

Although the above compounds for many years used as a dispersant, especially as additives in the composition of the pesticide compositions, there is a need to increase the dissolution rate of such compounds, without prejudice to such performance characteristics as suspendida ability and the e, more than 11 minutes Although this is sufficient for the end use pesticide compositions, such a result is not ideal.

Such nonionic surfactants as EO/PO-block copolymers, combined with anionic surfactants. U.S. patent 5169894, issued in the name Holland et A1., refers to the dispersant for suspensions of inorganic pigment with polycarboxylate and nonionic EO/PO-block copolymer surfactants. In these cases, the nonionic surfactant is used to reduce anionic load on the pigment, and the polyacrylate is a major component of the mixture, the proportion of which can reach 90%. Holland et al. do not describe how, provides enhanced dissolution rate of nonionic surfactants adding thereto anionic component.

U.S. patent 5169894 is the closest analog of the present invention in relation to dispergating mixture. The closest analogue of the agricultural composition is a UK application 2230954 A, describing the pesticidal composition comprising a pesticide and dispergating mixture of a polymer with surfactant ve the Institute one or more dispersing agents, derived from EO/PO-block copolymer surfactant mixtures, with a significantly higher dissolution rate and superior performance properties.

The present invention is the creation of the formulation of the dispersant to the water environment, with an increased rate of dissolution.

Another objective of the invention is to provide mixtures of nonionic ethylene oxide/propyleneoxide block copolymers with anionic polymers and surfactants for use as a dispersant with a higher dissolution rate.

The next objective of the invention is to provide an improved dispersant for use in agriculture, particularly in pesticide compositions.

In addition, the present invention is to increase the dissolution rate EA/copolymer surface active dispersing agents without significant effect on their performance.

The task of the invention is solved in that dispensatory mixture consisting of block copolymers of ethylene oxide and propylene oxide containing at least 70% ethylenoxide links, and polyacrylates, with the ratio of components wt.%:

block copolymers of ethylene oxide and propylene oxide containing at least 70% ethylenoxide links - 85-92

the polyacrylate - 5-12

at least one linear Las - 0,1-5

when the total content of all components is 100 wt.%.

Dispergator mixture according to the invention is extremely effective when used in agriculture, primarily as a dispersant for pesticide compositions.

In this regard, another the problem is solved by the development of agricultural pesticide composition that includes a pesticide and dispergating mixture of a polymer with a surface-active agent of the following composition, wt.%:

block copolymers of ethylene oxide and propylene oxide, comprising 70-80% ethylenoxide links - 85-92

the polyacrylate - 5-12

at least one linear Las - 0,1-5

when the total content of all components is 100 wt.%.

The task is also solved by a method of increasing the dissolution rate of the block-copolymer of ethylene oxide and propylene oxide, in the exercise of which a block copolymer of ethylene oxide and of propylene oxide added an effective amount of a polyacrylate and at the of iMER can be increased by approximately 50% or more.

Dispensatory mixture in accordance with various implementation of the invention includes at least one nonionic ethylene oxide/propylenoxide (EO/PO) block copolymer surfactant component of the following formula:

< / BR>
where x, y and x' represent such numbers that the share ethylenoxide (EA) component accounts for more than about 50%, more preferably more than about 70% of the total molecular mass (MW), and where MWpropylenoxide (hydrophobe is from about 950 to about 4000 (in all cases, except as specifically stated, all molecular weight in the present description is expressed in the form srednevekovyh molecular mass or MW). It is desirable that the molecular weight of each of these compounds was in the range of from about 6000 to about 15000 or, even more preferably in the range of from about 9000 to about 15000. Especially preferred EO/PO-block copolymers form part series products PLURONICsupplied to the market by BASF Corporation. Especially preferred is an EO/PO-block copolymer represented by the above formula, the molecular mass of which is equal priblizitelen as EO/PO-block copolymers can also be used PLURONICF128 with a molecular mass of approximately 12600 and PLURONICF108 with a molecular mass of approximately 14,600.

The share of non-ionic surface-active component accounts for 85 to 92 wt.% dispergating mixture (in all cases, unless otherwise specified, the content expressed in mass% of total mass of the mixture or composition). In a more preferred embodiment, the proportion of EO/PO-block copolymer ranges from 88 to 92%. In an even more preferred embodiment, the proportion of nonionic copolymer surfactant ranges from 89 to 90 wt.% by weight of the total surfactant mixture.

Also part dispergating mixture according to the invention is one or more anionic polymers. Such anionic polymer component of the mixture includes one or more of polycarboxylates. In a preferred embodiment, such polycarboxylate are polyacrylates. Especially preferred those polyacrylate, molecular weight less than or equal to approximately 12,000. Preferred polyacrylates with a molecular weight from about 1200 to about 8000. Particularly preferably, one of the anionic components are mixed to the 4000. This compound is marketed by BASF Corporation under the trademark SOKALANPA-30.

The above-mentioned anionic polyacrylate component (s) dispergating mixture is contained in an amount of from 5 to 12% of the mixed composition. In the preferred embodiment, this component is from about 8 to about 12% of such compositions. In a particularly preferred variant of the share of the above anionic component accounts for up to approximately 10% of the mixed composition. The mass percentage of the polyacrylate component in the present description expressed in terms of percentage activitiesthese substances, such as polyacrylates usually dissolve in water.

In addition, part dispergating mixture in accordance with the invention is one or more anionic compounds selected from the group comprising linear alkylbenzenesulfonate. It was found that the addition of relatively small amounts of at least one line of Las to a mixture of nonionic surfactants with above the anionic polyacrylate polymer significantly increases the dissolution rate (as described on the 8-C18-alkylbenzenesulfonates. More preferred are those compounds in which an alkyl group is representative of the C8-C15-Akilov. Particularly preferred linear C12-C15-alkylbenzenesulfonate, including mixtures thereof.

Linear alkylbenzenesulfonates component of this mixed composition is from 0.1 to 5% of the whole mixture. In a more preferred embodiment, this component is contained in the composition in an amount of from 0.1% to 2.5%. More effective those mixtures which contain linear Las, with C12-C15-alkyl group, in an amount of from 0.5 to 1.5%. In one particularly preferred variant of linear Las is approximately 1% of all mixed composition.

To a person skilled in the art it is obvious that for the preparation of mixed composition surfactant/polymer in accordance with different variants of execution of the invention can, if necessary in the beginning to melt EO/PO-block copolymer surfactant component, since such compounds are usually found in solid or pasty condition. Then this component is thoroughly mixed with policebox the Institute. After mixing, the mixture is placed on a cold surface, such as stainless steel chamber for storage of frozen products for solidification of the melt. Then this mixture can be pelletized or to punish in the mill for further use or analysis.

The time of dissolution of the mixture of surfactant/polymer in accordance with the invention in water is less than approximately 6.5 minutes In the preferred embodiment, this time of dissolution is less than about 6 minutes Scope of the invention also includes that the claimed mixture of surfactant/polymer is dissolved in water for less than about 5.5 minutes the Term "time of dissolution" in the context of the present description is used to denote a parameter defined as follows.

190 g of water with Ca/Mg-rigidity 342 frequent./million poured into 400 ml of chemical glass. Water is slowly stirred with a magnetic stirrer, is not causing the formation of a crater. Add 10 g of a mixture of surfactant/polymer in the form of a sieve fraction of particles 14-20 mesh (1.41 to 0.84 mm) and include a stopwatch. The operation of dissolution stop, when to the naked eye no longer distinguish between the tree of time.

The following examples are all listed in the description of the examples are designed to illustrate one or more aspects of the invention, therefore, they should not be construed as limiting its scope.

Example 1.

Example 1 (as follows from the data in table. 1; table. 1 and 2, see below) illustrates the time of dissolution in minutes for various preferred embodiments of the invention, which is true also for the comparative examples.

Any expert in the art may be noted that the time of dissolution 1. only one EO/PO-block copolymer nonionic surfactant exceeds 11 minutes Adding polycarboxylate to the block copolymer in 2.) and 3.) increases the rate of dissolution. Thus, for any expert in the art it is obvious that adding only one polycarboxylate to EO/PO-block copolymer nonionic surfactant is included in the scope of the invention. Adding a line to Las mixtures 4.), 5.) and 6.) the dissolution rate increases markedly. The time of the dissolution of all mixtures 4.), 5.).and 6.) is less than about 6.5 minutes

The mixture of surface-Actis active solid materials, in particular pesticides in pesticide compositions. This pesticide can be any product, known to experts in the art, including, for example, the connection atrazine (2-chloro-4-ethylamino-6-isopropylamino-8-triazine). It is obvious that the term "pesticide" shall also include any other appropriate means, such as fungicides, herbicides and biocides, and in these examples, the list is not limited.

The actual pesticide is usually from about 70 to about 99.9% of the pesticide composition, preferably from about 80 to about 92%.

This pesticide composition additionally contains a mixture of surfactant/polymer in accordance with its various options, which are presented in the present description, in quantities of from 0.1 to 12% of the pesticide composition, preferably in amounts from 1 to 10%. In accordance with a particularly preferred variant of this pesticide composition contains from 2 to 8% of a mixture of surfactant/polymer.

This pesticide composition may also contain wetting agents, and other substances known in the art. The remainder of the pesticide composition is isconsistently cultures, etc. in the field of agricultural consumer usually adds in dosed quantities of water.

Example 2.

Example 2 shows that the operating characteristics of different pesticide granular compositions containing dispergator mixture of surfactant/polymer according to the invention, they have a minimal impact, or in some cases have really enhance the effect in comparison with the characteristics of the same songs as the dispersant contain only EO/PO-block copolymer surfactant. Was prepared following the granular material.

90% of atrazine or

92% of atrazine

3% wetting agent BASOWETBX

2% wetting agent BASOWETBX

7% SURFACTANT

3% SURFACTANT

2% filler clay BENTONITEHMP-20

1% residual moisture

The procedure for preparation of the aforementioned granulated material was carried out as follows. Portions were mixed in a V-shaped mixer and crushed before sieving through a sieve with mesh size of 0.022 inch (0.56 mm). The crushed material was granulated on a 16-inch (406.4 mm) tray at an angle of 60o. Gran the IPA was tested by determining the size of particles wet sieve analysis, the hardness, suspenderbelt, time wetting, separation and re-suspension. The results obtained are presented in table. 2.

It can be assumed that a mixture of surfactant/polymer according to the invention, with an increased rate of dissolution may also find use as a dispersant in other areas that use ethylene oxide/propyleneoxide block copolymers, the rate of dissolution which must be improved.

Although the invention is described with an illustration of each of the different variants of its implementation, it is assumed that a person skilled in the art can make some modifications, while staying within the essence and scope of the invention defined by the description and the appended claims.

1. Dispensatory mixture consisting of block copolymers of ethylene oxide and propylene oxide containing at least 70% ethylenoxide links, and polyacrylates, characterized in that it additionally contains at least one line of Las in the following ratio, wt.%:

Block copolymers of ethylene oxide and propylene oxide containing at least 70% of this is - 0.1 to 5

when the total content of all components is 100 wt.%.

2. The mixture under item 1, characterized in that it contains at least one line of Las in the amount of 0.5 - 5 wt.%.

3. The mixture under item 1, characterized in that it contains a block copolymer of ethylene oxide and propylene oxide of molecular weight more than or equal to about 6000.

4. The mixture under item 1, characterized in that it contains a polyacrylate of molecular weight about 1200 - 12000.

5. The mixture under item 1, characterized in that it contains a line of Las with C8- C18is an alkyl group.

6. The mixture under item 1, characterized in that it contains a block copolymer of ethylene oxide and propylene oxide in the amount of 88 to 92 wt.%.

7. The mixture under item 1, characterized in that it contains polyacrylate in an amount of 8 to 12 wt.%.

8. The mixture under item 2, characterized in that it contains a line of Las in an amount of 0.1 - 2.5 wt.%.

9. Mix on p. 3, characterized in that it contains a block copolymer of ethylene oxide and propylene oxide of molecular weight of about 8400 89 - 90 wt.%.

10. The mixture according to p. 4, characterized in that it contains a polyacrylate molecules line Las, with C12- C15-alkyl group, in the amount of 0.5 - 1.5 wt.%.

12. Agricultural pesticidal composition comprising a pesticide and dispergating mixture of a polymer with surface-active substance, characterized in that dispensatory mixture contains, in wt.%:

Block copolymers of ethylene oxide and propylene oxide, including 70 - 80% ethylenoxide links - 85 - 92

The polyacrylate - 5 - 12

At least one linear Las - 0,1 - 5

when the total content of all components is 100 wt.%.

13. The way to increase the dissolution rate of the block-copolymer of ethylene oxide and propylene oxide, wherein the block-copolymer of ethylene oxide and of propylene oxide added an effective amount of a polyacrylate and at least one line of Las.

14. The method according to p. 13, characterized in that the use of polyacrylates of molecular weight about 1200 - 8000.

15. The method according to p. 13, characterized in that as the linear alkylbenzenesulfonates use C12- C15-alkylbenzenesulfonate or mixtures thereof.

 

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