KR810000277B1 - Herbicidal compositions - Google Patents

Abstract

A herbicidal compn. based on bipyridilium cmpds. contain RCOOH (I; R = OH, halo, carboxyl, alkoxycarbonyl, carbamoyl, substitutable C1-4 alkyl with N-lower alkyl substituted carbamoyl) such as n-valeric acid, n-butylic acid as the olfactory alerting agent in order to avert inadvertent poisoning. Thus, a formulation contained paraquat dichloride containing quaternary cationic salt (II; [X n- = anion; n = 1-4 integer), and I besides surfactants, preservatives and H2O.

Description

Herbicide composition

The present invention is a component having a unique odor added to prevent the accidental drinking of herbicidal bipyridylium tetrachloride and herbicidal bipyridylium tetrachloride as an active ingredient (e.g., n- gil acetic acid, iso- or n- Butyric acid).

Following the discovery of the insecticidal properties of DDT, the synthesis of hormonal herbicides was carried out by 2,4-dichlorophenoxyacetic acid, and a wide range of pesticides were developed for agriculture to remove groups, pests and weeds. While this substance is certainly toxic to certain forms of life, there is no harm to human life if used according to proper care and nationally recognized laws. Despite encouraging the adoption of safe handling involving pesticides, there is a risk of misuse of pesticides. One particular dangerous example is when a handler transfers a small amount of concentrated solution into a household container such as a beverage bottle for later use at home. The danger with this practice is when a child or careless adult accidentally finds the disease and drinks content that may have dangerous consequences.

British patent specification 1,406,881 discloses a herbicide consisting of an odorant consisting of a pyridine base consisting of a mixture of an aqueous solution of herbicidal bipyridylium tetracationic salts and an alkylpyridine. The unpleasant odor of the malodorant acts as a warning that the component is not a beverage and the malodorant consequently reduces the accidental drinking of this herbicide in the circumstances described above.

The choice of malodorants to be mixed with bipyridylium tetravalent cationic herbicides is greatly limited by the exact technical requirements that malodorants must meet. For example, the odorant must be sufficiently dissolved in the concentrated bipyridylium solution, be able to be physically and chemically miscible, have a long enough storage stability and have an odor that is not confused with the unique odor of other commercial products. do.

The use of the bases of the pyridine described above burdens the manufacturer because it requires the inspector to inspect the components whether the pyridine base component varies according to its source and the component conforms to the appropriate standards.

It was confirmed that a component having satisfactory retardance can be obtained by appropriately changing the composition of the bipyridylium solution containing carboxylic acid, which is a malodorant previously considered unsuitable as a malodorant.

The present invention provides a method for preparing a concentrated herbicide composed of an aqueous solution of a malodorous agent (pH 5 or less) containing a herbicidal bipyridylium tetravalent cation salt and an alkylcarboxylic acid. The unpleasant odor of the odour acts as a warning that the ingredient is not a beverage.

The term alkylcarboxylic acid means a compound of the general formula RCOOH, wherein R is a straight or branched chain alkyl group containing 3-5 carbon atoms.

Preferred alkylcarboxylic acids for use as components of the present invention are n-butyl acid (I) iso-butyl acid (II) and n-gilnoic acid (III).

The component is preferably in the range of pH 1-5 and preferably also contains a surfactant. Preferred herbicidal bipyridylium tetrachloride used as a component of the present invention is represented by the following general formula.

Food,

R and R ¹ can be the same or different,

R and R ₁ are alkyl groups of 1-4 carbon atoms substituted with hydroxyl, halogen, carboxyl, lower alkoxy, lower alkylcarbonyl, lower alkoxycarbonyl, carbamoyl or N-lower alkylsubstituted carbamoyl, [X] ^n- represents an anion, n is an integer of 1-4, lower alkoxy, alkoxycarbamoyl, alkylcarbonyl, alkyl is a group containing an alkyl group having 1-4 carbon atoms. Particularly preferred herbicidal bipyridylium tetrachloride is as follows.

1,1'-dimethyl-4,4'-bipyridylium di (methylsulfate), (para quat methosulfate)

1,1'-ethylene-2,2'-bipyridylium dibromide (diquat dibromide)

1,1'-dimethyl-4,4'-bipyridylium dichloride (paraquat dichloride)

1,1'-di-2-hydroxyethyl-4,4'-bipyridylium dichloride

1-2-hydroxyethyl-1-methyl-4,4'-bipyridylium dichloride

1,1'-di-carbamoylmethyl-4,4'-bipyridylium dichloride

1,1'-bis-N, N-dimethylcarbamoylmethyl-4,4'-bipyridylium dichloride

1,1'-dimethyl-4,4'-bipyridinium sulfate (paraquat sulfate)

1,1'-bis-N, N-dimethylcarbamoylmethyl-4,4'-bipyridylium dichloride

1,1'-Diacetonyl-4,4'-bipyridylium dichloride

1,1'-diethoxycarbonylmethyl-4,4'-bipyridylium dibromide

1,1'-diaryl-4,4'-bipyridylium dibromide

The name in () beside some of the compounds mentioned above is a recognized generic name for the cationic portion of this compound. Thus, paraquat is the generic name for 1,1'-dimethyl-4,4'-bipyridylium cation. Paraquat is a particularly preferred bipyridylium compound for use as a component of the present invention. Since the herbicidal effect of bipyridium tetracationic is irrelevant to the nature of the integrated anion, the choice of anion according to the price is not a problem and an anion that easily generates a water-soluble salt is preferable. Examples of monovalent or polyvalent anions include acetate, benzenesulfonate, benzoate, bromate, bromide, butyrate, chlorate, chloride, citrate, formate, florosilicate, fumanate, flororate, iodide , Lactate, maleate, maleate, methylsulfate, nitrate, propionate, phosphate, salicylate, sulfamate, succinate, sulfate, thiocyanate, tarrate and P-toluenesulfonate. Herbicidal bipyridylium cation salts are formed from a number of similar anions or other anionic compounds, with salts having any particular desired anion either directly synthesized from a reactant containing the desired anion or passed through a solution of a pre-prepared salt through an ion exchange resin. It is prepared by replacing the anion of the salt prepared in advance and the desired anion by a known method. In terms of economics, chloride anions are particularly preferred anions.

Since the specific herbicidal action of herbicidal bipyridylium tetravalent cation salts is present only in the cation, it is customary to specify the amount of bipyridylium cation used when defining the concentration of active ingredient or the cost of use. The inconvenience of having to quote different usage rates for the separate salts of the bipyridylium tetravalent cation is avoided.

The use ratios and concentrations cited in this specification relate to the amount of bipyridylium tetravalent cation unless otherwise specified.

The amount of herbicidal bipyridylium tetravalent cation present as a component of the present invention is preferably 0.5-3.0 pounds (50 g-300 g / l) per Imperial gallon, and 1.0- per imperial gallon. 2.5 pounds (100-250 g / l) is more preferred. Surfactants can be cationic, nonionic or anionic. Generally, anionic surfactants react with each other bipyridylium tetrachloride in the component, so cationic surfactants and nonionic surfactants are not suitable for use as components of the present invention. Active agents are preferred over anionic surfactants.

지방산과 헥시톨무수물로부터 유도된 부분 에스테르, 예컨대 소비탄 모노라우레이트 에틸렌옥사이드와 상기 부분에스테르와의 축합생성물과 레시틴이 있다. 양이온성 계면활성제의 예로는 4가염과 에틸렌옥사이드와 아민과의 축합물이 있으며, 예컨대 상기물질들은 ＂에토민(Ethomeen)＂, 에토듀오민(Ethoduomeen)＂, 듀오콰드(Duoquad)＂와 아트콰드(Arquad)＂라는 등록상표하에 판매된다.Examples of nonionic surfactants used as components of the present invention are condensation products of alkylphenols such as octylphenol, nonylphenol and octylcresol with ethylene oxide, and other anionic surfactants are long chains.

Partial esters derived from fatty acids and hexitol anhydrides such as sorbitan monolaurate ethylene oxide and condensation products of said partial esters with lecithin. Examples of cationic surfactants include tetravalent salts and condensates of ethylene oxide with amines. For example, these materials include Ethtomine, Ethoduomeen, Duoquad and Artquad. (Arquad) ＂is sold under the trademark.

Particularly preferred surfactants are combinations of the surfactants described in British Patent No. 998,264 for the preparation of herbicidal bipyridylium tetrachloride.

The amount of surfactant present in the component of the invention is preferably 20-100 g per liter of the component.

The choice of odorants for use in water-soluble compositions composed of herbicidal bipyridium salts is not straightforward. For economical reasons for transportation and storage it is desirable that the composition be sold in the form of a concentrate and that it can be diluted with water when required as a solution of a suitable concentration for use of the concentrate. These concentrates may contain 5% -20% (wt%) of herbicidal bipyridylium tetravalent cations, because many of the materials do not mix or dissolve in bipyridium salt solutions at such concentrations. As a result, excess odorant floats on the concentrate surface. This results in a homogeneous distribution of malodorants when the concentrate is repackaged from large vessels to smaller vessels. Insoluble materials are therefore unsuitable as odorants. Furthermore, the odorant should not react chemically with the active ingredient, and when reacting, it lowers the herbicidal properties of the active ingredient. In the preparation of herbicidal concentrate, it is inevitable that several months have passed before it is used, so that the odorant should not be deteriorated in long-term storage. In the present invention, two years of storage experiments revealed that an unpleasant odor was maintained.

The component of the present invention preferably contains 0.5-5% (wt%) of the alkylcarboxylic acid used as the odorant and more preferably 1% -4% (wt%) of the alkylcarboxylic acid used.

Due to the low pH of the components of the present invention, the formulations of the present invention are corrosive. It must be handled carefully so that it does not splash on the eyes or skin, and must not come into contact with corrosive metals before dilution.

The components of the present invention also comprise colored dyes and pigment compounds.

Examples of compounds used in the practice of the present invention include Monastral Blue BNV paste and Lissimine Turquoise VN 150.

Example 1

This example describes a component of the present invention consisting of 1% W / V of n-gil acetic acid which acts as an odorant in aqueous solution, the components of which are as follows.

Element% W / V

Paraquat Concentration X

Sodium mataborate 1.3

Sodium benzoate 2.0

Lisapol NX 1.1

D S 4392 4.1

Silcolapse M5000 0.06

n-gilacetic acid 1.0

Based on water 100

(X is 200 ± 5g / liter paraquation)

pH 3.5 ± 0.5 Specific gravity 1.05-1.12

Paraquat concentrate is a paraquat dichloride solution containing 25% -30% (wt%) of 1,1'-dimethyl-4,4'-bipyridylium cation. The amounts specified in the table above are sufficient to contain 20% (by weight) of paraquat cations. pH was adjusted to pH 3.5 by addition of concentrated hydrochloric acid. Lissapol® NX is a registered trademark of a surfactant consisting of a condensate of 7 mol-8 mol ethylene oxide and 1 mol P-nonylphenol. DS 4392 is the code number of a surfactant consisting of an amine mixture derived from conjibalic acid condensed with approximately 15 moles of ethylene oxide.

Silcolapse is a registered trademark of an antifoaming agent consisting of silicone derivatives. The aforementioned components are prepared by stirring the components together.

Example 2

This example describes the components of the present invention consisting of a concentrated aqueous solution of iso-butyl acid (4% W / V) as a odorant, the components of which are as follows.

(Where X is 200 ± 5 / liter paraquat ion)

pH 3.5 ± 0.5 Specific gravity 1.05-1.12

The components of the present invention are prepared in the same manner as in Example 1.

Example 3

This example describes a component of the present invention consisting of a concentrated aqueous solution comprising n-butyl acid (4% W / V) as an odorant, the component of which is as follows.

(Where X is 200 ± 5 g / liter paraquat ion)

pH 3.5 ± 0.5 Specific gravity 1.05-1.12

The components of the present invention are prepared in the same manner as in Example 1.

Example 4

This example describes a component of the present invention consisting of a concentrated aqueous solution containing n-gil acetic acid (1% W / V) as an odorant, the component of which is as follows.

Element% W / V

Paraquat Concentrate X

n-gilacetic acid 1.0

(Where X is 200 ± 5 g / liter paraquat ion)

pH 3.5 ± 0.5

The components of the present invention are prepared in the same manner as in Example 1.

Claims (1)

As described above in the text, an aqueous solution of an odorant which is an alkylcarboxylic acid of the herbicidal bipyridylium tetravalent cation salt of the following general formula and general formula RCOOH, wherein R is a straight or branched chain containing 3-5 carbon atoms ( concentrated herbicidal composition consisting of less than pH 5).

Wherein R and R ¹ may be the same or different, and may be substituted with hydroxyl, halogen, carboxyl, lower alkoxy, lower alkylcarbonyl, lower alkoxycarbonyl, carbamoyl or N-lower alkylsubstituted carbamoyl Alkyl group having 1-4 carbon atoms, [X] ^n- is an anion and n is an integer of 1-4.