CN1344136A

CN1344136A - Process and compsns. promotijng biological effectiveness of exogenous chemical substances in plants

Info

Publication number: CN1344136A
Application number: CN99816339A
Authority: CN
Inventors: G·G·索拉; R·梅吕克斯; A·J·L·勒梅西耶; P·G·凯瑟; A·J·I·瓦德; J·L·吉勒斯皮; R·J·布林克
Original assignee: Monsanto Co
Current assignee: Monsanto Co
Priority date: 1998-12-23
Filing date: 1999-12-17
Publication date: 2002-04-10
Also published as: CA2356556A1; AU2201700A; MXPA01006571A; BR9916573A; AR029323A1; ZA200104632B; EP1139737A1; JP2002533356A; WO2000038514A1; ID30398A

Abstract

A plant treatment composition for application of an anionic exogenous chemical substance such as glyphosate to foliage of a plant is provided. The composition comprises, in addition to the exogenous chemical substance, one or more amine compound(s) each having formula (I) wherein R<1> is a hydrocarbyl group having 6 to about 22 carbon atoms and at least about 30 % of all R<1> groups present have 14 to about 22 carbon atoms, and R<2> and R<3> are independently C1-5 hydrocarbyl groups. The amine compound(s) of formula (I) are present in the composition in a mole ratio to the exogenous chemical substance of about 0.01:1 to about 0.8:1. The exogenous chemical substance and amine compound(s) of formula (I) are dissolved or dispersed in an agronomically acceptable liquid carrier, preferably water. Also provided is a solid or liquid concentrate composition which, upon dissolution or dispersion in, or dilution with, water, forms a plant treatment composition of the invention. Plant treatment compositions of the invention are useful for eliciting a biological activity, for example herbicidal activity, in a plant.

Description

Promote the composition of the method for the biopotency of xenobiotics in plant

Invention field

The field that the present invention relates to is the xenobiotics that is administered on the plant leaf blade, and particularly a kind of method and the composition of using by this method are used to promote the biopotency of described xenobiotics.

A kind of natural or synthetic chemical substance that obtains of term used herein " xenobiotics " expression, this material is administered on the plant to show the biologically active of hope.Term used herein " biologically active " be illustrated in the plant in being present in plant or on pathogen, parasite or consumer organism in releasing stimulus, inhibition, adjusting, treatment, toxicity or lethal response.The example of xenobiotics includes but not limited to chemical pesticide (as weed killer herbicide, algicide, fungicide, bactericide, virucide, insecticide, miticide and invertebrate poison), plant growth regulator, fertilizer and nutrients, gametocide, defoliant, desiccant, its mixture etc.

Term used herein " biopotency " expression is passed through to plant leaf blade administration of exogenous chemical substance, the bioactive degree of express wishing, or as selecting expression to produce to express to the application dosage or the rate of application of the required xenobiotics of biologically active of the hope of predetermined extent.For example, when xenobiotics was weed killer herbicide, biopotency can cause the inhibition degree of plant growing by the weed killer herbicide of using specified quantitative, or by producing specific inhibition degree, for example 50% or 85% amount of application that suppresses required weed killer herbicide is measured.Therefore the increase of the biopotency of weed killer herbicide or enhancing can be expressed as the reduction of the required weed killer herbicide minimum amount of a certain threshold value that for example increase of plant growing inhibition level or generation plant growing suppress under the specified rate weed killer herbicide.

Background technology

For the multinomial purpose of agricultural and related endeavors, wish to handle plant with various xenobioticses.Have many xenobioticses to be applied on the plant leaf (being blade and other non-wooden acrial parts), and the action site in plant near or away from the dispenser point.Above-mentioned substance is referred to herein as the foliage applying xenobiotics.

Usually, when the plant treatment method that suppresses by this area is applied to leaf with xenobiotics, has only the application point in the fraction application of substances arrival plant, at the expection biological activated energy effective expression of this application point xenobiotics.Therefore, a main hope in agricultural and related endeavors is to strengthen the efficient that the foliage applying xenobiotics is transferred to its application point in plant, and therefore strengthens the biopotency of xenobiotics for its application target.

By means known in the art xenobiotics is administered to leaf and can produce the invalid application point that transfers at large.Said method provides outstanding biopotency in some cases, even under the low consumption of xenobiotics.In other cases, use the xenobiotics of same amount that inadequate biopotency only is provided.Therefore, these methods are being inconsistent aspect its result who provides, and perhaps they differ provides expected results surely.

A problem is may pre-determine those hardly can obtain the situation that good biological is renderd a service, and the reason of part is to have several factors to influence efficiency of transmission.These factors comprise weather before, during and after the dispenser (temperature, relative moisture, day long, cloud amount, rainfall, wind etc.), device-dependent inaccuracy and other factors in soil regime (fertile degree, ventilation etc.), plant growing stage, health and physiological situation, the dispenser.Therefore, for helping to guarantee the reliable or consistent biopotency of foliage applying xenobiotics, in most of the cases, the user generally can use this material to be higher than real essential consumption.

Be acid and generally be mixed with water soluble salt that wherein under the situation that this xenobiotics exists with anionic form, the changeability of its biopotency under field condition is the problem of a special trouble at xenobiotics.Sometimes by above-mentioned acidic materials are changed into ester, can control this changeability; Yet the biopotency that shows of ester reduces in many cases, for example owing in case transform back original acid deficiently at processed inside plants.To strengthening the foliage applying xenobiotics, particularly the reliability of the biopotency of anion xenobiotics and biopotency still keeps strong needs.

Term used herein " anion xenobiotics " represents that a kind of xenobiotics, its molecular structure comprise one or more acid or supply the proton site, and therefore can form a kind of anion in the presence of proton acceptor.Therefore this term comprises the material of both sexes.When a kind of xenobiotics is described as " anion " of this paper, be not to hint that this xenobiotics must be anionic form or free.

Provide the benefit of the method for more reliable biopotency to comprise the amount of application that can reduce xenobiotics, and need not to sacrifice the continuity of biopotency.The pressure that the reduction agricultural chemicals that agribusiness experienced, especially weed killer herbicide use can pass through to be proved about the meeting of this theme, as hold by Weed Science Society of America and be documented in WeedTechnology 8,331-386 (1994).Reduce consumption and not only bring the repayment of environment aspect, and bring the repayment of economic aspect, because the cost of per unit processing area has reduced.

The xenobiotics of foliage applying often and amphiprotic substance, particularly amophoteric surface active reagent or is called surfactant and uses together.Surfactant can influence the biopotency of the xenobiotics of foliage applying in every way.

When the Aquo-composition of the xenobiotics of dilution being administered to the blade face with conventional hydraulic atomizing, surfactant can change the particle diameter distribution of spray droplet in the existence of the Aquo-composition of dilution, generally can increase the percentage of droplet form sprayed volume, reduce the percentage of big drop form sprayed volume.Because the momentum of droplet is less than big drop, these droplets are unlikely to rebound from blade surface, therefore more may be retained on this surface.Also can promote the spraying confining force by the adhesion of surfactant molecule in the spray droplet and blade surface, this blade surface in most plants be wax with hydrophobic.This adhesion not only reduces resilience, and can reduce spray droplet and run off from plant surface.Surfactant also is easy to increase the contact area between spray droplet and the blade surface, can also strengthen xenobiotics as a rule and infiltrate from drop and pass the blade epidermis and arrive the inner vanes tissue.

For a long time, known that the amphiprotic substance that comprises surfactant by these and perhaps other effects in addition, can increase the biopotency of xenobiotics.Therefore in order to obtain acceptable physical stability or serviceability, comprising one or more surfactants in the commodity preparation of the xenobiotics of foliage applying is common phenomenon as for example emulsifier or suspending agent or dispersant, even in the preparation that does not need surfactant to exist.

Strengthen the viewpoint of biopotency effect from surfactant, one of foliage applying anion xenobiotics of broad research is a herbicide glyphosate.Glyphosate has been used as plant growth regulator and phytotoxicity agent.

Say that from the viewpoint of strictness glyphosate (N-phosphonomethylglycine) is a kind of acid compound, but except context indicate in addition, " glyphosate " of this paper uses from non-limiting viewpoint, not only comprise glyphosate, also comprise its salt, adduct and its ester and in plant tissue, can change into glyphosate or the compound of glyphosate ion can be provided on the contrary.In the commodity preparation of most of glyphosates, glyphosate exists with the form of water soluble salt.At this on the one hand, glyphosate is typical acid or forms anionic outermost exogenous chemical substance.

The salt of weeding glyphosate is disclosed in for example U.S.3799758 of Franz, the U.S.3853530 of Franz, the U.S.4140513 of Prill, the U.S.4315765 of Large, the U.S.4405531 of Franz, the U.S.4481026 of Prisbylla and the U.S.4507250 of Bakel.In most of disclosed salt, the counter ion counterionsl gegenions of glyphosate anion are low-molecular-weight relatively non-ampholytic cations.Typical this salt is alkali metal, for example sodium and sylvite; With many ammonium, sulfonium, cationic salt of sulfoxonium of containing, described cation is contained the organic group that amounts to 1-6 carbon atom by 1-3 and replaces, for example Dimethyl Ammonium.Isopropyl ammonium, ethanol ammonium and trimethyl sulfonium salt.

The commodity preparation of glyphosate salt comprises, for example the Roundup of Monsanto company ^Trade mark, Accord ^Trade mark, Roundup ^Ultra trade mark and Round ^The weed killer herbicide of Xtra trade mark, above-mentioned weed killer herbicide contains the isopropyl ammonium salt.The Roundup of Monsanto company ^Dry trade mark and Rival ^The weed killer herbicide of trade mark, above-mentioned weed killer herbicide contains ammonium salt.The Roundup of Monsanto company ^Geoforce trade mark weed killer herbicide, this weed killer herbicide contain the Touchdown trade mark weed killer herbicide of sodium salt and Zeneca, and this weed killer herbicide contains the trimethyl sulfonium salt.

The ampholytic cation salt with higher molecular weight of glyphosate also discloses.This ampholytic cation comprises those cations that have hydrophilic segment such as ammonium, ethanol ammonium, polyoxyethylene ammonium or sulfonium base and contain the hydrophobic part of 1-4 the alkyl that totals over 6 carbon atoms.For example, above-cited U.S.4405531 disclose many glyphosates primary, the second month in a season and tertiary amine salt, cation wherein is the cation of both sexes mentioned above and its molecular weight less than about 300, this patent disclosure is incorporated herein by reference.Example comprises C _6-18Alkyl ammonium cation.International publication number WO83/03608, European Patent Application No. 0124351, European Patent Application No. 0360181 and U.S.4431594 disclose the quaternary ammonium salt of various glyphosates, and cation wherein is both sexes.U.S.5668085 discloses the glyphosate salt with ampholytic cation, and described ampholytic cation derives from polyoxyethylene three C _8-22Alkylamine surfactant, N-coconut alkyl-N that concrete disclosed example is a glyphosate, N-diethanol ammonium salt, wherein " coconut alkyl " refers to be mainly C ₁₂And C ₁₄Alkyl chain is derived from the mixture of cocoa butter.The european patent application of above quoting 0124351 discloses a kind of salt of glyphosate, the trialkylamine of cation source wherein, i.e. and dimethyl dodecyl ammonium salt, and point out that the preferred mol ratio of alkylamine and glyphosate is 1: 1.The european patent application of above quoting 0360181 also discloses the glyphosate salt of cation source in similar trialkylamine, in this case, the alkylamine in the dimethyl coconut alkylammonium salt that calculates and the mol ratio of glyphosate are in all cases greater than 1: 1.

Glyphosate has many advantages, particularly environmental advantages as weed killer herbicide, comprises biodegradability and low environment toxicity.Yet, can not effectively glyphosate be delivered to the site that glyphosate is brought into play its phytotoxicity effect in the plant even studies show that the effective glyphosate formulation of biology that uses at present.Usually, the weed killer herbicide that has only sub-fraction to use arrives above-mentioned site.

The glyphosate that has only fraction to use arrives the phytotoxicity action site must be relevant through multiple combination obstacle with glyphosate.Wherein, most important one is lipophilic epidermis on using the blade surface of glyphosate.Therefore glyphosate is put into the both sexes medium is desirable to inference, and described both sexes medium can make between lipophilic epidermis and the hydrophilic glyphosate more compatible, promotes glyphosate to infiltrate thus and passes through epidermis.Similar viewpoint has been applied to other xenobioticses, and particularly those generally are mixed with the material of water soluble salt.

Use the both sexes medium as the supplementary means of epidermis infiltration and for example strengthen thus that the notion of the biopotency of glyphosate is effectively by many studies have shown that, in described research by using surfactant to strengthen Foliage Absorption or validity.Wyrill ﹠amp; The broad research of Burnside, Weed Science 25,275-287,1977 draw the conclusion of " effectively surfactant is the key component of any glyphosate Spray Mixing thing ", but notice the greatest differences of different surfactant types between the enhancing weeding validity degree degree that it provides.Usually, cationic surfactant provides stronger humidification than anion surfactant.At Wyrill ﹠amp; Be alkylamine surfactant Armeen between the disclosed surfactant of Brunside ^TMDM12D and Armeen ^TMDM16D is called dodecyl dimethyl amine and hexadecyldimethyl benzyl ammonium amine.Test only much larger than the molar concentration of glyphosate molar concentration (for Armeen ^TMDM12D, alkylamine/glyphosate mol ratio is 10.5: 1 and 21: 1; For Armeen ^TMDM16D, alkylamine/glyphosate mol ratio is 8.3: 1 and 16.6: 1) under carry out Wyrill ﹠amp; Brunside finds that these surfactants are being relative nullity aspect the enhancing activity of weeding; Yet the surfactant TD-692 (alkylamine/glyphosate mol ratio is 6.8: 1 and 13.5: 1) that is called the dodecyl dimethyl ammonium succinate is more effective.Within the scope of the present invention, those skilled in the art are easy to accept to strengthen xenobiotics according to surfactant under the high surfactant level, and particularly the bioactive relative effectivenes of glyphosate can not be predicted reliably than the relative effectivenes under the low surfactant level.

International open WO98/06259 write down with the data of the form of mixtures of glyphosate composition or many cations, nonionic, anion and the amphoteric surfactant after glyphosate, used in turn.

It is with glyphosate and lipophilic agent that another kind provides the method for both sexes medium, uses with the form of water-in-oil emulsion or microemulsion together as oil.Described emulsion or microemulsion are disclosed in European patent application EP 0379852, U.S.4853026 and U.S.5248086.The shortcoming of described microemulsion is when providing concentrated composition, at water it is diluted to the concentration that is fit to use such as 5g/L (ga.e./l) glyphosate when (representing with acid equivalent), can run into the ruined phenomenon of emulsion.In other words, the water-in-oil microemulsion agent is unable to undergo dilute with water.Described microemulsion can not provide the epidermis permeability of improvement perhaps can not stand to dilute relevant with it.

Also studied the thick emulsion of oil-in-water (macroemulsion) of glyphosate.In these thick emulsions, most of glyphosate exists with continuous water form, for example shown in the European patent application EP 0485207.Therefore this glyphosate is that the thick emulsion that separates can not provide the glyphosate of amphoteric form with lipotropic component, and can not strengthen the transmittability of glyphosate to its phytotoxicity action site in plant usually.

Exemplified a kind of diverse ways in the European patent application EP 0148169, this method is by the interfacial polycondensation effect water soluble herbicide such as glyphosate to be enclosed in the polymer shell.In the method, used the water-in-oil emulsion that contains based on the lipophilic emulsifier of alkylated polyvinyl pyrrolidone.The polymerisation that reaction by comonomer forms shell occurs on the oil-water interface of the emulsion that contains weed killer herbicide, and the result forms the shell of sealing this weed killer herbicide.

It is believed that wherein glyphosate is followed a kind of N-(C _6-22) alkyl-N, N-two (C _1-5) composition of alkyl ammonium compounds or its salt only disclose wherein amines and the mol ratio of glyphosate be at least 1: 1 (European patent application EP 0124351 and the EP0360181 that quote as mentioned) on the contrary or be low especially situation.For example, international open WO97/16969 discloses glyphosate composition, has wherein added minor N-decyl-N, and the N-alkyl dimethyl ammonium chloride is to strengthen the stability of said composition in the presence of more substantial another kind of surfactant.Concrete disclosed N-decyl-N, the N-dimethyl amine is about 0.02: 1 to the high molar ratio of glyphosate.

All methods of above-outlined comprise the method that the anion xenobiotics is mixed with the salt of both sexes, thereby limited in the achievement that obtains when xenobiotics transferred to its biological agent site in plant of overcoming obstacles.Therefore, an object of the present invention is to provide a kind of xenobiotics, particularly the new composition or the preparation of anion xenobiotics can provide good biopotency when it is administered to plant leaf surface.

That another object of the present invention provides a kind of economy and make simple, the xenobiotics particularly composition or the preparation of anion xenobiotics.

Another object of the present invention provides and a kind ofly can satisfy above-mentioned purpose composition or preparation, particularly when it is applied to herbicide glyphosate, can keep the non-ambient toxicity and the biodegradability characteristic of glyphosate simultaneously.

Another object of the present invention provides a kind of xenobiotics, the particularly composition of anion xenobiotics or preparation, and described composition or preparation can be applicable in the aqueous medium, and can not lose its useful performance under the highly diluted rate.

Another object of the present invention provides a kind of Aquo-composition or preparation of amphoteric salt form of anion xenobiotics, even described composition or preparation also are physically stable, and do not need extra stabilizing agent such as dispersant or emulsifier under high concentration.

Another object of the present invention provides easily a kind of and economic method and prepares the composition or the preparation that can satisfy above-mentioned purpose.

These and other purposes can transfer in the plant by the blade face to promote the anion xenobiotics by designing a kind of new method, and promote the biopotency of this xenobiotics to be met thus.The more fully statement hereinafter of this method.

Description of drawings

Fig. 1 is the transmission electron micrograph according to the aqueous compositions of the amphoteric salt of the N-phosphonomethylglycine of embodiment 1 preparation.The calibration lines are represented 100nm.This microphoto is represented supramolecular aggregation, shows as globule spherical in shape substantially, diameter from about 20 to about 100nm.The limit of resolution of generally acknowledging transmission electron microscope used herein is about 20nm, although therefore believe have littler supramolecular aggregation to exist, they are invisible in the microphoto of this microphoto or Fig. 2.

Fig. 2 is the transmission electron micrograph according to the aqueous compositions of the amphoteric salt of the N-phosphonomethylglycine of embodiment 6 preparations.The calibration lines are represented 100nm.This microphoto is represented supramolecular aggregation, shows as globule spherical in shape substantially, diameter range from about 20 to about 100nm.

Fig. 3 is the graphic representation according to the particle diameter distribution of the emulsion grain in the composition of embodiment 7 preparations.

Summary of the invention

Newly provide a kind of and be used to be administered on the plant leaf surface, comprise the amines of a kind of anion xenobiotics and one or more formulas (I) to cause the plant treatment compositions of biological respinse:

R wherein ¹Be alkyl, preferred linear alkyl chain contains 6 to about 22 carbon atoms, and the R of all existence ¹At least 30% of group is to contain the 14 above-mentioned alkyl to about 22 carbon atoms of having an appointment, R ²And R ³Be C independently _1-5Alkyl.When with about 10 consumptions to about 1000 liters of per hectares (l/ha) said composition being administered to plant leaf surface, the amount that contains xenobiotics in the composition should be enough to cause biological respinse.The mol ratio of the formula that contains in the composition (I) amines and xenobiotics is about 0.01: 1 to about 0.8: 1, preferably approximately 0.05: 1 to about 0.8: 1, and more preferably from about 0.1 to about 0.5: 1.The amines of this xenobiotics and formula (I) is dissolved or dispersed in agricultural and goes up acceptable liquid-carrier, in the preferred water.

In first embodiment of the present invention, composition comprises a kind of moisture application media, and supramolecular aggregation is colloidal dispersion in wherein.Supramolecular aggregation comprises one or more amphoteric salts, this amphoteric salt contains the cation that the protonation of the amines of the anion of anion xenobiotics and passing type (I) obtains, in first embodiment, contain the xenobiotics of three kinds of molal quantities in the composition:

(a) the first molal quantity X ¹, neutralized by described amines;

(b) the 0 or second molal quantity X ², removed the neutralization first molal quantity X ¹Amines beyond the neutralization of one or more alkali; With

(c) the 0 or the 3rd molal quantity X ³, with the form of the acid that do not neutralized by any alkali.

This paper reference (be X with the form of salt or the molal quantity that is existed by the anion xenobiotics that alkali neutralizes ¹And X ²) be based on and suppose that unreacted bronsted lowry acids and bases bronsted lowry can not coexist as in the composition, but and do not mean that this hypothesis must be correct or effective.In fact, the Acid-Base N-process of believing the amphoteric salt that provides above-mentioned is coexistence complicated and that can cause unreacted bronsted lowry acids and bases bronsted lowry.So molal quantity X used herein ¹Or X ²Be to determine by the molal quantity that suitable alkali exists, do not consider the part of the alkali of (i) protonated or cationic form, (ii) be the part of the xenobiotics of anionic form by deprotonation, or (iii) this alkali and the xenobiotics degree of in composition, associating or dissociating.Molal quantity X ³Refer to surpass and be contained in X ¹Or X ²The unneutralized acid of molal quantity.

X ¹, X ²And X ³The following mensuration of interpolation molal quantity of amines and other alkali by xenobiotics and formula (I).

1. when xenobiotics has only an energy to be not more than the total mole number of xenobiotics existence by the interpolation total mole number of the acidic-group of deprotonation and alkali, at this paper X ¹Be defined as the molal quantity that equals formula (I) amines, X ²Equal the molal quantity of other alkali.X ³Deduct (X by the total mole number that exists from xenobiotics ¹+ X ²) draw.

2. has not only an energy when being not more than the total mole number that xenobiotics exists at xenobiotics, X by the interpolation total mole number of the acidic-group of deprotonation and alkali ¹, X ²And X ³As above-mentioned 1 definition.

3. at xenobiotics when to have not only an energy be 1-2 times of the total mole number that exists of xenobiotics by the interpolation total mole number of the acidic-group of deprotonation and alkali, X ³Be defined as 0.As (X ¹+ X ²) a part of X ¹Be defined as the molal quantity that equals to add formula (I) amines of a total mole number part as alkali.In other words, if formula (I) is if the interpolation molal quantity of amines is the interpolation molal quantity of a and other alkali is b, then

X ¹/(X ¹+X ²)＝a/(a+b)，

With

X ²/(X ¹+X ²)＝b/(a+b)

In this first embodiment, if there is the xenobiotics of second molal quantity, then this part xenobiotics preferably can be provided one or more alkali neutralizations of monovalent cation, described cation is selected from organic ammonium or the sulfonium cation that alkali metal cation, ammonium cation, total contain 1-6 carbon atom, with the trialkyl ammonium cation, each alkyl wherein contains 4-6 carbon atom.

In second technical scheme of the present invention, composition comprises a kind of moisture application media, in this medium is dissolving or the anion xenobiotics that disperses and the amines of formula (I), wherein aforesaid supramolecular aggregation can be selected to exist, but does not have the amphoteric salt existence of xenobiotics in this supramolecular aggregation substantially.Preferably in second embodiment, xenobiotics is the form of water soluble salt, and counter cation wherein is low-molecular-weight, and the amines of each formula (I) is the form of the salt that forms with acid, and this acid is not xenobiotics as herein described.More preferably the counter cation of xenobiotics salt is the cation of monovalence, is selected from alkali metal cation, ammonium cation and contains organic ammonium and the sulfonium cation that amounts to 1-6 carbon atom." low-molecular-weight " expression molecular weight in the counter cation scope is lower than about 100.

Require in second embodiment in composition of the present invention, " do not have the existence of xenobiotics amphoteric salt substantially " and satisfied in following situation in supramolecular aggregation: (1) does not have the supramolecular aggregation existence substantially or can be discerned by method disclosed herein; (2) can discern and have supramolecular aggregation, but determine not contain substantially xenobiotics by technology known in the art; Or (3) can discern and have supramolecular aggregation, but determine that by technology known in the art all basically xenobioticses are present in the aqueous medium.

Therefore second embodiment of the present invention may be interpreted as plant treatment compositions, is used to be administered to plant leaf surface to cause biological respinse, and said composition is moisture, wherein dissolves or be dispersed with the amines of anion xenobiotics and one or more formulas (I):

R wherein ¹Be alkyl, preferred linear alkyl chain contains 6 to about 22 carbon atoms, and the R of all existence ¹At least 30% of group is to contain the 14 above-mentioned alkyl to about 22 carbon atoms of having an appointment, R ²And R ³Be C independently _1-5Alkyl; Wherein when with about 10 consumptions to about 1000 liters of per hectares (l/ha) said composition being administered to plant leaf surface, the amount that contains xenobiotics in the composition should be enough to cause biological respinse; Wherein the mol ratio of the formula that contains in the composition (I) amines and xenobiotics is about 0.01: 1 to about 0.8: 1, preferably approximately 0.05: 1 to about 0.8: 1, and more preferably from about 0.1 to about 0.5: 1; Wherein said composition comprises a kind of moisture application media, wherein there is not the supramolecular aggregation that is colloidal dispersion substantially, described supramolecular aggregation is to contain one or more amphoteric salts, and this amphoteric salt contains the cation that the protonation of the amines of the anion of xenobiotics and passing type (I) obtains.

In a preferred embodiment of the invention, also comprise a kind of assistant agent compound in the aforesaid plant treatment compositions, the molecular structure that this compound has comprises one and contains about 2 polyoxyethylene chains to about 100 ethylene oxide unit(s)s, the weight ratio of this assistant agent compound and xenobiotics is about 1: 10 to about 10: 1, preferred about 1: 3 to about 3: 1.

The preferred N-phosphonomethylglycine of anion xenobiotics that can be used for the above-mentioned arbitrary embodiment of the present invention.

A kind of concentrate composition also is provided, when said composition is dissolved or dispersed in the water of appropriate amount, or during with the water dilution of appropriate amount, can forms aforesaid plant treatment compositions.This concentrate composition can be solid or liquid.The solid concentrate composition of expection amounts to and to contain at least about 5 weight % and about at the most 75 weight % or the above xenobiotics of representing (a.e.) with acid equivalent.The liquid concentrating composition of expection amounts to and to contain at least about 5 weight % and at the most 50% or the above xenobiotics of representing (a.e.) with acid equivalent.

A kind of method for preparing the liquid concentrating composition of first embodiment of the invention also is provided, comprises neutralization procedure and regulating step.

Neutralization procedure is included in the preferred water-bearing media of liquid by stirring amines with one or more formulas (I) the first molal quantity X that neutralizes ¹The anion xenobiotics contain the fluid composition of the amphoteric salt of one or more these xenobioticses with manufacturing.This neutralization procedure can be selected also to comprise by stirring and introduce the second molal quantity X in this fluid composition ²Xenobiotics, this xenobiotics be except by the neutralization the first molal quantity X ¹The form of one or more salt beyond the amphoteric salt that forms.Can select and be independent of second molal quantity of existence, the 3rd molal quantity X ³Xenobiotics be that form with acid exists and be not neutralized.The salt of the xenobiotics of second molal quantity can by before neutralization first molal quantity, in or after, by being stirred in the liquid medium with this second molal quantity original position manufacturing that neutralizes of one or more alkali; As selection, described salt can by means known in the art prepare respectively and before first molal quantity neutralization, in or after add in the liquid medium.

Regulating step comprises that continuing to stir this fluid composition is colloidal dispersion in liquid medium until supramolecular aggregation, and described supramolecular aggregation comprises the amphoteric salt with the xenobiotics that forms with xenobiotics in the amines of formula (I).

In case of necessity can among above-mentioned any procedure of processing, before or after add other compositions of said composition immediately, assistant agent compound for example, the molecular structure that this compound has comprises one and contains at least about 2 polyoxyethylene chains to about 100 ethylene oxide units.

When the molecular structure that has when the anion xenobiotics had only an acid position, term " neutralization " was interpreted as representing the acid that waits mixed first or second molal quantity of alkali of molal quantity with basic.The molecular structure that has when the anion xenobiotics is during by two or more acid position, the situation of N-phosphonomethylglycine for example, term " neutralization " are interpreted as representing that acid with mixed first or second molal quantity of about 1-2 moles base per mole acid is to form monovalent salt, divalent salts or its mixture.

Very clear in addition term used herein " neutralization " only refers to the mixed of bronsted lowry acids and bases bronsted lowry, may not mean that whole bronsted lowry acids and bases bronsted lowry reactions forms salt.

The alternative approach for preparing liquid concentrating composition of the present invention comprises the step of preparation first concentrated aqueous solution or aqueous dispersion, this aqueous solution or aqueous dispersion contain the salt of anion xenobiotics and low-molecular-weight counter cation, second concentrated aqueous solution or the step of aqueous dispersion and the step of mixed first and second concentrated solutions or dispersion formation liquid concentrating composition that prepare the acid salt of the amines that contains formula (I).Can select by adding composition that entry regulates so preparation composition with the final concentration that obtains wishing.In case of necessity can among above-mentioned any procedure of processing, before or after add other compositions of said composition immediately, assistant agent compound for example, the molecular structure that this compound has comprises one and contains at least about 2 polyoxyethylene chains to about 100 ethylene oxide units.

Can measure the product of this optional method by method disclosed herein, whether exist colloidal dispersion in aqueous medium supramolecular aggregation and be determined at whether there is xenobiotics in described supramolecular aggregation and/or the aqueous medium by means known in the art.The result of described mensuration can determine that whether this product is the composition of first or second embodiment as mentioned above.

" concentrate " aqueous solution or dispersion and be interpreted as having at least 5 weight % concentration at this paper, but being no more than the xenobiotics that is expressed as acid equivalent of Cmax or the amines of formula (I), is unsettled, uneven or immobilising (for example gel or paste) at this composition that obtains more than Cmax.The concentrated aqueous solution of general salt contains the salt of about 10 weight % to maximum percentage by weight, and this maximum percentage by weight is corresponding 20 ℃ solubility limit with this salt.

First concentrated aqueous solution or the dispersion that are used for above-mentioned alternative approach can be commodity, the MON 0139 of Monsanto company for example, and this product is the glyphosate isopropyl ammonium salt aqueous solution of 62 weight %.As selection, this first concentrated aqueous solution or dispersion can be dissolved or dispersed in the water by the salt solid with xenobiotics, or prepare by xenobiotics is reacted in aqueous medium with its sour form and suitable low-molecular-weight alkali.

Second concentrated aqueous solution or the dispersion that are used for above-mentioned alternative approach can be commodity, perhaps can be by initial unprotonated formula (I) amines is prepared with suitable acid reaction in aqueous medium.

In the mixed step of above-mentioned alternative approach, relative quantity with the expection mol ratio that calculates amines that liquid concentrating composition Chinese style (I) can be provided and xenobiotics adds first aqueous solution or dispersion in second aqueous solution or the dispersion, vice versa, and this process is preferably by stirring.

The preparation method of solid concentrate composition of the present invention comprises anion xenobiotics or the mixture of its salt or this anion xenobiotics and salt thereof and the amines of one or more formula (I) of the first step with solid particulate form, mixed to form the wet-mixing thing with the water of capacity simultaneously, its denseness should be suitable for one or multinomial further operation described below.In this mixed step, can comprise other compositions, assistant agent compound for example, the molecular structure that this compound has comprises that contains about 2 polyoxyethylene chains to about 100 ethylene oxide unit(s)s.The amines of formula (I) and xenobiotics are mixed to calculate the relative quantity that can be provided at expection mol ratio in the solid concentrate composition.Under low relatively mol ratio, for example about at the most 0.3: 1, the wet-mixing thing of formation was suitable for further processing, and need not the existence of any solid inert carrier; But under higher mol ratio, find probably must comprise solid inert carrier so that obtain the wet-mixing thing of expection denseness.The appropriate amount of each composition can be determined by routine test by those skilled in the art in the mixed step.

This method comprises that also second step formed wet bonded particulate and dry this particle of the 3rd step with this wet-mixing thing granulation.Any method of granulating of the water-soluble or water-dispersible granular material of suitable preparation xenobiotics known in the art all can use; Method for optimizing is dish granulation and extruding pelletization.Can use any drying means of the water-soluble or water-dispersible granular material of suitable preparation xenobiotics known in the art; Method for optimizing is a fluid-bed drying.

The change of said method will be apparent to those skilled in the art.Composition of the present invention is not limited to those compositions by the clear and definite disclosed method manufacturing of this paper.

Also provide a kind of in plant or in being present in plant or on pathogene, parasite or consumer organism in cause bioactive method, comprise step to the plant treatment compositions of the foliage applying biologic effective dose provided herein of plant.

The composition of expection has one or more benefits or advantage as described below.At least composition of the present invention provides the useful alternative of previously known preparation.

When being administered to the blade face according to method of the present invention, to compare with the commercialization standard preparation of same xenobiotics, the biopotency that the composition of expection provides has strengthened.Under identical xenobiotics amount of application, the composition of expection can cause stronger biological respinse than commercialization standard preparation.Be to obtain the biological respinse of setting level, this xenobiotics uses with the form of contemplated composition that to use the amount of application that needs than the form of commercialization standard preparation lower.

Compare with the commercialization standard preparation, contemplated composition has biopotency to the target species of wide spectrum more setting under the amount of application.

Compare with the commercialization standard preparation, contemplated composition can both provide more reliable or more coherent biopotency under many environmental conditions.

Compare with the commercialization standard preparation, the more anti-rain of contemplated composition (rainfast), promptly its biopotency is unlikely owing to the rainfall or the artificial rainfall that occur in a short time reduce, after described short-term is for example used about at the most 6 hours.

Compare with the commercialization standard preparation, contemplated composition provides visible biological respinse in can be after using shorter time.

Specifically, have surprisingly been found that with list (N-decyl-N, the N-Dimethyl Ammonium) salt of pure substantially xenobiotics and compare that compositions display of the present invention goes out better or more effective biopotency.

Detailed Description Of The Invention

Xenobiotics

The example that can be used for the anion xenobiotics of the present composition comprises, but be not limited to, chemical pesticide (as weed killer herbicide, algicide, fungicide, bactericide, virucide, insecticide, aphicide, miticide, nematocide and invertebrate poison), plant growth regulator, fertilizer and nutrients, gametocide, defoliant, desiccant, its mixture etc.Although content disclosed herein relates to " a kind of xenobiotics ", and is very if desired clear, in composition of the present invention, can comprises and surpass a kind of xenobiotics.

The preferred anionic surfactants xenobiotics is by the chemical substance of general postemergence application to plant leaf surface, and promptly foliage applying anion xenobiotics is formed.Particularly preferred foliage applying anion xenobiotics is made up of the material of absorption in the plant, promptly is transferred to its usually other parts the plant of the biological agent of its expection of performance from its inlet point at blade to a certain extent.

Wherein particularly preferably be weed killer herbicide, plant growth regulator and nematocide, particularly molecular weight less than those materials of about 300, do not comprise counter ion counterionsl gegenions in the described molecular weight.

In these compounds, preferred kind is made up of nematocide, as is disclosed in U.S.5389680, and its disclosure is incorporated herein by reference.This organizes preferred nematocide is 3,4,4-three fluoro-3-butenoic acids or N-(3,4,4-three fluoro-1-oxygen-3-cyclobutenyls) glycine.

In one embodiment, xenobiotics is a weed killer herbicide.The non-limiting acifluorfen that comprises of suitable weed killer herbicide, the spirit of sulphur grass, the diformazan Herbicidal compositions, Bentazon, bilanafos, bromacil, Brominal, fluorine ketazolam grass, Amiben, morpholine acid dichloride picoline, 2,4-D, 2,4-DB, dalapon, dicamba, 2,4-drips propionic acid, diclofop-methyl, the bacterium polyacid, Fenac, fenoxaprop-P, FLAMPROP, fluazifop, Flumiclorac pentyl, fluoroglycofen-ethyl, fomesafen, kill wooden phosphorus, Glufosinate, glyphosate, fluazifop-butyl, cigarette imidazoles grass, miaow grass ester, imazamox, imizapic, the weed eradication cigarette, the weed eradication quinoline, Imazethapyr, ioxynil, MCPA, MCPB, Vi par, methanearsonic acid, alanap, n-nonanoic acid, picloram, dichloro quinolinic acid, quizalofop-ethyl, sulfamic acid, 2,3,6-TBA, TCA and triclopyr.Particularly preferred weed killer herbicide is the weed killer herbicide that its molecular structure comprises at least a amine, carboxylate and phosphonate or phosphinate functional group.This weed killer herbicide comprises N-phosphonomethylglycine (glyphosate) and DL-high lactamine-4-base (methyl) phosphinate (Glufosinate).Another organizes preferred weed killer herbicide is imidazolone type, comprises cigarette imidazoles grass, miaow grass ester, imazamox, imizapic, weed eradication cigarette, weed eradication quinoline and Imazethapyr.

The present invention specifically describes with reference to glyphosate.Therefore although glyphosate has three acid positions, and can form trivalent salt, it is about 8 that the pH value of preferred Aquo-composition is not more than, and in this pH value, the part that exists with the trivalent salt form in the glyphosate is little of ignoring.Therefore this paper only considers that two are significantly removed protonated acid position when pH8.One of them is the phosphonate part at the glyphosate molecule, and another is at carboxylate moiety.

For the convenience of this paper and succinct, sometimes glyphosate is called GH ₂The monovalence glyphosate anion as dominant in the pH4 left and right sides, is called as GH ^-The divalence glyphosate anion as dominant at pH7-8, is called as G ^2-

In plant treatment compositions of the present invention, the content of the xenobiotics of form of ownership should be enough to cause the biologically active of expection when being administered to plant leaf surface.Said composition is called as " spray composite ", " can spray composition " or " promptly using composition " sometimes and generally contains the extremely xenobiotics of about 2 weight % of 0.02 weight % of having an appointment, and this material is represented (a.e.) with acid equivalent.In some occasion, said composition can contain about at the most 5 weight %a.e. or even 10 weight %a.e..

In concentrate composition of the present invention, the content of the xenobiotics of form of ownership should be enough to diluting, forming when being dissolved or dispersed in the proper volume water plant treatment compositions, and this plant treatment compositions is administered to plant leaf surface to cause the biologically active of expection.Liquid concentrating composition contains the 5 weight % that have an appointment to about 50 weight %a.e. or more xenobiotics, and described xenobiotics refers to the existence form that they are all.Solid concentrate composition contains the 5 weight % that have an appointment to about 75 weight %a.e. or more xenobiotics, and described xenobiotics refers to the existence form that they are all.

Because the pith of packing concentrate composition cost is and the relevant cost of volume of packing, transportation and storage, therefore wishes to increase maximum feasible concentration range or " load " of xenobiotics in composition.Usually the factor of confined liquid composition load is the physical stability of said composition under multiple storage condition.The upper limit of load depends on the character of other compositions in the composition and concentration and can use means known in the art easily to determine by routine test.

In disclosed first embodiment of the invention above, the xenobiotics part exists with the form of its salt, and this salt contains one or more formulas (I) amines as counter cation.In disclosed second embodiment above, these salt are not the compositions that can know identification in the composition, and the xenobiotics of introducing is the form of salt, and this salt contains molecular weight and is lower than about 100 counter cation, or the mixture of described salt.In the preferred salt of this second embodiment, counter cation be monovalence and be selected from organic ammonium and the sulfonium cation that alkali metal cation, ammonium cation and total contain 1-6 carbon atom.

Be in the situation of glyphosate at this xenobiotics particularly, the exemplary counter cation that is applicable to the composition of second embodiment of the invention is sodium, potassium, ammonium, Dimethyl Ammonium, isopropyl ammonium, an ethanol ammonium and trimethylsulfonium cation.

In this specification, unless context has requirement in addition, all places that relate to xenobiotics generally are specially adapted to glyphosate.

The amines of formula (I)

As mentioned above, composition of the present invention contains the amines of one or more formulas (I):

R wherein ¹Be alkyl, preferred linear alkyl chain contains 6 to about 22 carbon atoms, R ²And R ³Be C independently _1-5Alkyl.In the general formula of this amines, R ¹Preferably contain at least 10, more preferably at least 12, at least 14 carbon atoms most preferably.Yet, in all embodiments of the present invention, all R ¹At least 30% of group contains at least 14 carbon atoms.R ²And R ³Preferred C _1-3Alkyl, most preferable.More preferably R ¹Be the saturated or unsaturated chain that contains 14,16 or 18 carbon atoms, R ²And R ³It is methyl.Common R ¹Chain derives from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linolenic acid, linoleic acid or other natural acids.In the particularly preferred amines, the R1 chain derives from myristic acid, palmitic acid, stearic acid or oleic acid.

Usually in composition of the present invention, only use the amines of a kind of formula (I).Yet, because the R of this amines ¹Group often derives from natural resources such as cocoa butter, palm oil, butter etc., and the commodity preparation of this amines contains the hydrocarbon chain length of certain limit, changes with degree of unsaturation sometimes.For example " coconut alkyl " compound contains the R that derives from cocoa butter ¹Group, this group mainly are C ₁₂Saturated (lauryl or dodecyl) and C ₁₄Saturated (myristyl or myristyl) chain.Equally, " tallow alkyl " compound contains the R that derives from butter ¹Group, this group mainly are C ₁₈Unsaturated (oil base) and saturated (stearoyl or octadecyl) and C ₁₆Saturated (cetyl or cetyl) chain.Therefore, when the quantity of the amines of this paper limitation type (I), know that very this quantity comprises the amines of other formulas (I) that exist in the used amines preparation.

Particularly preferred formula (I) amines comprises N-coconut alkyl-N, N-dimethyl amine, available Noram ^TMDMC D, N-stearoyl-N, N-dimethyl amine, available Noram ^TMThe main component of DMSH D, N-oil base-N, N-dimethyl amine, available Noram ^TMDMO D and N-tallow alkyl-N, N-dimethyl amine, available Noram ^TMDMS D, all products are all from the CECA S.A. of Paris, FRA.

Xenobiotics at least part by N-coconut alkyl-N, N-dimethyl amine, for example commodity Noram by name ^TMThe product of DMC D can satisfy all R under the situation of neutralization ¹At least 30% of group contains the requirement of 14 carbon atoms.Although dominant hydrocarbon chain length is C in the fatty acid of cocoa butter (the coconut alkyl is obtained from this raw material) ₁₂, but in cocoa butter C ₁₂More the maximum level of short chain is 70%.Therefore at least 30% coconut alkyl is C ₁₄Or longer chain.See R.T.Morrison ﹠amp; R.N.Boyd, Organic Chemistry, sixth version (1992), Prentice Hall, the 1121st page.Surprisingly, found and be disclosed in the N-dodecyl-N that contains pure glyphosate in the European patent application EP of above quoting 0124351, the composition of N-dimethyl ammonium is compared, contain by using N-coconut alkyl-N, the compositions display of the salt mixture that obtains with glyphosate in the N-dimethyl amine goes out stronger herbicide action.Believe this good effectiveness and C ₁₄More the alkyl of long-chain is at N-coconut alkyl-N, and the distribution in the N-dimethyl amine is relevant, and these alkyl are pure N-dodecyl-N, and are unexistent in the N-dimethyl ammonium.

Sometimes the amines of formula (I) is represented with its protonated (cation) form in this article, maybe when following anion xenobiotics or other counter anion, used A ⁺Representative.Know very much the A that this paper relates to ^-Quantity comprise all quantity with the not protonated amines compound of acid as the coexistence of the xenobiotics of sour form.

In composition of the present invention, the amines of its Chinese style (I) is introduced with the form of its salt, this salt is to form with a kind of acid except that xenobiotics, and every kind of amines is all by protonated and be present in the aqueous solution or the dispersion with the counter anion of following.Suitable counter ion counterionsl gegenions include, but are not limited to chloride, bromide, iodide, sulphate, ethosulfate, phosphate, acetate, propionate, succinate, lactate, citrate and tartrate.

In above-mentioned composition, can there be the salt of amines in theory, the counter anion in this salt is this exogenous active substance itself.Estimate that this salt shows as amphiprotic substance in aqueous medium; For example, can expect generally can become supramolecular aggregation to be present in the composition by autohemagglutination after this salt surpasses finite concentration that this aggregation contains the part xenobiotics.Yet, the present invention do not require this amphoteric salt can discern ground (identifiably) as one independently kind exist, or the discernible existence of this supramolecular aggregation, if or this aggregation exist, this supramolecular aggregation contains described amphoteric salt.

Therefore, in second embodiment of the invention described above, determining not have substantially supramolecular aggregation by method disclosed herein exists, or define supramolecular aggregation according to means known in the art and exist, but the salt of amine-containing compound not substantially, the counter anion of described salt is an xenobiotics.

For example, preparation of compositions of the present invention is that the low molecular weight salts of anion xenobiotics such as isopropyl ammonium glyphosate are joined in the moisture aqueous colloidal dispersion of supramolecular aggregation, described dispersion contains the hydrochloride of the amines of formula (I), as N-oil base-N, the N-alkyl dimethyl ammonium chloride.Use the chloride electrodes selective, can be before adding glyphosate salt and measure the concentration of chlorion free in the aqueous medium afterwards.If the concentration of chlorion does not increase, deducibility is arranged in the chloride of supramolecular aggregation is not replaced by glyphosate substantially, and therefore not having glyphosate substantially is arranged in supramolecular aggregation.In this case, said composition second embodiment according to the invention.More may record chlorine ion concentration increase in the aqueous medium, but ion exchange has taken place in inference in supramolecular aggregation thus, thereby in those aggregations, had the amines of formula (I) and the amphoteric salt of glyphosate.In this case, said composition first embodiment according to the invention but not second embodiment.

In the first embodiment, composition of the present invention contains amines by one or more formulas (I) the first molal quantity X that neutralizes ¹The anion xenobiotics and the amphoteric salt that forms.Said composition disclosed herein comprises first and optional second and/or the xenobiotics of the 3rd molal quantity, will more fully describe hereinafter.

The amphoteric salt of the xenobiotics of first molal quantity

The composition of first embodiment of the invention contains supramolecular aggregation, and this aggregation comprises the first molal quantity X that neutralizes of the amines by one or more formulas (I) ¹The anion xenobiotics and the amphoteric salt that forms.

For example, cation source can be represented by formula (III) in the both sexes monovalent salt of the glyphosate of the amines of formula (I):

[GH ^-][A ⁺]????(III)

And divalent salts, can represent by formula (IV):

[G ^2-][A ⁺] ₂???(IV)

Can there be formula (III) and amphoteric salt mixture (IV), and can select and glyphosate GH ₂And/or unprotonated amines exists jointly.

Even xenobiotics is a glyphosate usually, monovalent salt is also preponderated in the first embodiment, A ⁺Content (comprising not protonated amines compound) with acid coexistence preferably be no more than about 1mol/mol xenobiotics.Usually, for whole benefit of the present invention, A are provided ⁺Content should be enough to neutralize xenobiotics at least about 10%, promptly as (X ¹+ X ²+ X ³) a part, X ¹Preferably at least about 0.1.

Because the stable concentrate composition of preparation, wherein to contain the xenobiotics based on acid equivalent of high-load be one object of the present invention to said composition, therefore preferred conduct (X ¹+ X ²+ X ³) a part of X ¹Substantially less than 1, yet should be enough to provide biopotency, described biopotency equals the N-dodecyl-N of pure xenobiotics, the aqueous dispersion of N-dimethyl ammonium, i.e. X at least ²And X ³The biopotency of the composition of salt near 0.Usually this expression is as (X ¹+ X ²+ X ³) a part of X ¹Preferred about 0.1 to about 0.5.Work as A ⁺When the amines of cation source has higher molecular weight, unless the B of lower molecular weight ⁺Cation is preponderated, otherwise is difficult to the high-load that obtains to expect, described B ⁺Cation is sodium, ammonium or isopropyl ammonium cation for example.

For clarity sake, emphasize the X that defines in this specification and claims once more ¹, X ²And X ³Molal quantity is not to provide the amount of the xenobiotics of proton to determine by amines or other alkali to formula (I).On the contrary, the words of these molal quantitys alkali of only determining to were it not for excessive by the relative molal quantity of the amines of contained formula (I) in the composition and other alkali.This can obtain best explanation by example.

In this example, plant treatment compositions of the present invention contains the glyphosate 16.9ga.e./l of all acid and salt form, i.e. 100mM.Also contain N-lauryl-N, N-dimethyl amine (whole protonated and not protonated form) 5.3g/l, i.e. 25mM.And the sodium ion that is derived from sodium hydroxide, concentration is that 60mM is when representing with molar concentration, according to the first molal quantity X of glyphosate in this example of definition ¹Equal N-lauryl-N, the molar content of N-dimethyl amine, or 25mM.According to definition, the second molal quantity X of glyphosate ²Equal the content of sodium ion, or 60mM.The 3rd molal quantity X of glyphosate ³Determine by difference, i.e. (100mM-25mM-60mM)=15mM.

If there is excessive alkali, molal quantity X ³Be defined as 0.

But when xenobiotics is glyphosate, half that total interpolation molal quantity of preferred bases is the total molar content of glyphosate at least, and be no more than about 2 times.In other words, in preferred compositions:

If total molar content of the glyphosate of all salt and sour form is g;

If total molar content of formula protonated and not protonated form (I) amines is a;

If total molar content of the alkali of form of ownership is b except that formula (I) amines;

And if (a+b)/g represents by Z; So

(i)??0.05＜a/g＜0.8

(ii) 0＜b/g/1.95; With

(iii)0.5＜Z＜2。

Believe in the typical concentrated liquid composition of first embodiment of the present invention have for example to surpass about 10 weight % in a large number, preferably surpass the A that contains of about 50 weight % ⁺Cationic amphoteric salt is arranged in supramolecular aggregation, and this supramolecular aggregation is colloidal dispersion in liquid medium preferred water medium.This can be by separating supramolecular aggregation with means known in the art as filtering additive method centrifugal or disclosed herein from medium, and analyze two kinds of compositions that so obtain and confirmed.After the dilute with water concentrate composition is with the formation plant treatment compositions, has more amphoteric salts and be distributed in the aqueous medium; Even yet believe at present that in these cases in preferred compositions, most or whole basically amphoteric salts still remain in the supramolecular aggregation.

Not accepting opinion limits, it is believed that owing to amphipathic characteristic with the salt that makes with xenobiotics in the amines of one or more formulas (I), most of xenobiotics is arranged in supramolecular aggregation, this has explained at least in part and has passed through infiltration that improves or the ability that sees through epidermis, the good biopotency when the present composition is administered to plant leaf surface.

The salt of the second molal quantity xenobiotics

The second molal quantity X ²Xenobiotics show as one or more salt, this salt is different from and contains A ⁺Cationic salt.Described second molal quantity mainly is present in the supramolecular aggregation, in the water-bearing media or among both.This salt can be both sexes both sexes or non-.When the salt of second molal quantity is amphoteric salt, believe that it mainly is arranged in supramolecular aggregation.

The cation of the salt of the second molal quantity xenobiotics is generally provided by the alkali except that the amines of formula (I).Preferred cation formula monovalent cation, comprise (i) alkali metal for example sodium and potassium cationic, (ii) ammonium cation (iii) amounts to organic ammonium and the sulfonium cation that contains 1-6 carbon atom, (iv) trialkyl ammonium cation, each alkyl wherein all contains 4-6 carbon atom.

The cationic special example that can be used in the salt of the second molal quantity xenobiotics comprises sodium, ammonium, Dimethyl Ammonium, isopropyl ammonium, an ethanol ammonium, trimethylsulfonium and three hexyl ammonium cations.

The cation of the salt of the second molal quantity xenobiotics is called B sometimes jointly in this article ⁺Mixture with monovalent salt of this cationic glyphosate monovalent salt or glyphosate can be represented by formula (V):

[GH ^-][B ⁺]?????(V)

Can represent by formula (VI) with divalent salts or its mixture:

[G ^2-][B ⁺] ₂???(VI)

This paper relates to B ⁺Content be understood to include any content with the unionized or non-dissociated alkali of the xenobiotics of sour form coexistence.In most of occasions,, mainly monovalent salt in the preferred composition even xenobiotics is a glyphosate.

The xenobiotics of the 3rd molal quantity

The xenobiotics of the 3rd molal quantity can be selected to exist with the form of the acid that is not neutralized by any alkali.Usually, X ³The pact that accounts for the xenobiotics total mole number that exists with its form of ownership is half at the most.With (X ¹+ X ²) compare preferred X ³Be small, for example as (X ¹+ X ²+ X ³) a part of X ³Be not more than about 0.1.

The characteristic of contemplated composition

By selecting special amines disclosed herein, composition of the present invention can demonstrate the physical stability of height.When forming the colloidal dispersion of supramolecular aggregation, these dispersions of surprising discovery demonstrate the physical stability of height.Supramolecular aggregation itself and composition as a whole are physically stables, and this is a useful especially feature in a carrying at the present composition, storage and the use.

A unexpected especially discovery is if there is supramolecular aggregation, even this supramolecular aggregation still keeps its structural intergrity substantially when being diluted to the level that can be applied directly to plant leaf blade.This structural intergrity does not generally rely on the existence of dispersant or emulsifier, or the in fact existence of any surfactant except that formula (I) amines or its amphoteric salt.Yet as described below, the surfactant except that formula (I) amines or its amphoteric salt can be chosen wantonly and be present in the composition of the present invention.

Some moisture concentrate composition of the present invention can be described as the stable colloidal dispersion of supramolecular aggregation.About this point, " stablizing " expression composition does not stir storage at 20-25 ℃ and is not separated during 48 hours.Stability test more fully is described among the embodiment of this paper.The better moisture concentrate composition of the present invention is a colloidal dispersion, wherein to about 40 ℃ constant temperature or alternating temperature, be not separated during 48 hours without stirring storage at about 10 ℃, better is from about 0 ℃ to about 50 ℃ of constant temperature or the alternating temperature without stirring preservation 7 days, it would be desirable from approximately-10 ℃ be not separated 30 days without stirring preservation to about 60 ℃ of constant temperature or the alternating temperature.At high temperature stability in a short time provides good sign steady in a long-term under normal storage condition; Expect that some concentrate composition of the present invention can stablize 1 year or the longer time under normal storage condition.

Supramolecular aggregation composition of the present invention is called as " nanoparticles " sometimes.Term " nanoparticles " does not have received definition in this area; Yet when when this paper uses, this term refers to that longest dimension is the object of about at the most 1 μ m (1000nm), and comprises non-solid particle.

Contained supramolecular aggregation is two types at least in the present composition.First kind is too little so that the microphoto that can not detect and Fig. 1 and 2 can not be provided by transmission electronic microscope technology used in the certain embodiments of the invention, but can be by other technologies known in the art such as dynamic light scattering measurement.It approximately is the feature of globular micelle that first kind of supramolecular aggregation has, and its colloidal dispersion in aqueous medium is called as emulsion, microemulsion, micellar emulsion and micellar solution in every way.Unless context has requirement in addition, the term " emulsion " of describing the present composition is to prepare for such composition at this, and the micella in the said composition or other supramolecular aggregations also contain except that the amphoteric salt of xenobiotics oily in greater detail hereinafter.When lacking this oil, first type the micella or the average diameter of supramolecular aggregation generally are about 1 to about 10nm, and the most general is about 2 to about 5nm.

The same with other micellar dispersions, compositions display of the present invention goes out critical micelle concentration (CMC), and this concentration is the concentration of amphiprotic substance, can not assemble the formation micella at the molecule of the following amphiprotic substance of this concentration.The CMC that can not the amylase composition preferably has is no more than about 1000 μ M, more preferably no more than about 100 μ M.The method of measuring the CMC of the present composition provides in the embodiment of this paper.

The CMC value that the formula of glyphosate (I) tertiary amine compound amphoteric salt generally has is significantly less than and contains identical R ¹The corresponding salt that the primary amine of group forms.

Say that at least in part the special low CMC of preferred composition of the present invention can make supramolecular aggregation or micella can hold out against the level that can be used as spray composite that is diluted to.For example, the moisture concentrate composition that contains 169g/l (1 mole) glyphosate can provide the spray composite that contains the 10mM amphoteric salt when 100 times of dilute with waters, and wherein said glyphosate is all with the form of one (N-coconut alkyl-N, N-Dimethyl Ammonium) salt of its both sexes.Even having only 1% glyphosate in composition is the form of this amphoteric salt, and other glyphosates are forms of non-amphoteric salt, still greater than the CMC (37 μ M) of this salt, therefore still there is micella in the concentration of amphoteric salt behind 100 times of 100 μ M dilute with waters.

Aquo-composition of the present invention also can contain second kind of supramolecular aggregation.The size of these aggregations generally is 20-100nm and common as illustrated in fig. 1 and 2 sphere.They are too big so that can not be simple micella, believe on the multilayer shape that bubbles or the structure to be similar to liposome.

Moisture concentrate composition of the present invention generally is limpid or opaque slightly.

Other compositions

Composition of the present invention can contain acceptable material on the agricultural except that xenobiotics described herein or its salt.

For example, can comprise not only a kind of xenobiotics.The extra anion xenobiotics that can comprise be selected from for example above listed those.As selecting or in addition, can comprising the xenobiotics except that the anion xenobiotics of this paper definition.Glyphosate composition for example of the present invention can select to contain a kind of anion herbicidal compounds such as acifluorfen except that glyphosate, the spirit of sulphur grass, the diformazan Herbicidal compositions, Bentazon, bilanafos, fluorine ketazolam grass, morpholine acid dichloride picoline, 2,4-D, 2,4-DB, dalapon, dicamba, 2,4-drips propionic acid, diclofop-methyl, fenoxaprop-P, FLAMPROP, fluazifop, fluoroglycofen-ethyl, fluroxypyr, fomesafen, kill wooden phosphorus, Glufosinate, fluazifop-butyl, cigarette imidazoles grass, miaow grass ester, imazamox, imizapic, the weed eradication cigarette, the weed eradication quinoline, Imazethapyr, MCPA, MCPB, Vi par, methanearsonic acid, n-nonanoic acid, picloram, sulfamic acid, 2,3,6-TBA, TCA and triclopyr.Described extra anionic compound exists with the salt form that contains above-mentioned A-, and this salt can select to contain the B+ cation.Equally, the composition that the present invention contains the salt of anion weed killer herbicide can select to contain a kind of herbicides compounds except that the anion weed killer herbicide, as the ester derivant of anion weed killer herbicide, or be selected from following weed killer herbicide: Acetochlor, aclonifen, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azoles pyridine alkynes grass, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzofenap, bifenox, bromobutide, bromofenoxim, butachlor, butamifos, butralin, fourth oxygen cyclic ketones, butylate, benzophenone azoles, carbetamide, fluorine ketazolam grass, chlomethoxyfen, bromax, Pynamin, chlorimuronethyl, chlortoluron, Mo 9 granular, chlortoluron, chlorpropham, chlorine sulphur is grand, chlorthaldimethyl, chlorthiamide, cinmethylin, cinosulfuron, clethodim, alkynes oxalic acid, clomazone, clomeprop, the phonetic sulfanilamide (SN) salt of azoles, cyanazine, cycloate, AC322140, cycloxydim, cyhalofop-butyl, vanilla is grand, desmedipham, desmetryn, dichlobenil, diclofop-methyl, diflufenican, dimefuron, Youkebai, dimethachlor, dimethametryn, dimethenamid, dinitramine, dinoterb, diphenamide, dithiopyr, diuron, bacterium grass enemy, esprocarb, ethalfluralin, ethametsulfuron, etofumesate, ethoxysulfuron, diphenyl, fenoxaprop-P, fenuron, flampropmethyl, flazasulfuron, fluazifop, fluchloraline, Flumetsulam, Flumiclorac pentyl, flumioxazin, fluometuron, fluorochloridone, fluoroglycofen-ethyl, flupoxam, flurenol, fluridone, fluroxypyr-1-methylheptyl ester, flurtamone reaches careless fluorine, fomesafen, halosulfuronmethyl, haloxyfop-P-methyl, hexazinone, imazosulfuron, indanofan, isoproturon, isouron, isoxaben, different evil fluorine grass, isoxapyrifop, lactofen, lenacil, lorox, mefenacet, metamitron, metazachlor, methabenzthiazuron, methyldymron, metobenzuron, metobromuron, isopropyl methoxalamine, metosulam, metoxuron, piperazine humulone, metsulfuron-methyl, molinate, afesin, naproanilide, napropamide, quinclorac, neburea, nicosulfuron, norflurazon, orbencarb, oryzalin, the alkynes third oxazole grass, oxadiazon, it is yellow grand to encircle third oxygen, Oxyfluorfen, pebulate, pendimethalin, pentanochlor, penta oxazole grass, phenmedipham, piperophos, the third careless amine, primisulfuronmethyl, prodiamine, prometryn, prometryn, propachlor, Stam F-34, propaquizafop, propazine, propham, propisochlor, propyzamide, prosulfocarb, prosulfuron, the fluorine carfentrazone, pyrazolate, pyrazosulfuron, pyrazoxyfen, pyributicarb, pyridate, oxime pyridine grass, dichloro quinolinic acid, quinmerac, quizalofop-ethyl, rimsulfuron, sethoxydim, Tupersan, Simanex, symetryne, sulphur humulone, sulfentrazone, sulfometuronmethyl, lead ethyl xanthate is yellow grand, tebutam, tebuthiuron, terbacil, Te Dingtong, Garagard, P DimethenamidP, thrizopyr, thifensulfuronmethyl, benthiocarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron-methyl, trietazine, trefanocide, triflusulfuronmethyl and vernolate.

The xenobiotics that can be used for the present composition can be selected from canonical reference book such as ThePesticide Manual, the 11st edition, British Crop Protection Council (1997) and Farm Chemicals Handbook ' 97, those that Meister PublishingCompany (1997) is listed.

Also can comprise acceptable assistant or figuration material on the various agriculturals, no matter whether their purposes is directly to help the biopotency of xenobiotics in processed plant.For example, when xenobiotics is weed killer herbicide, can comprise liquid nitrogen fertilizer or ammonium sulfate in the composition.In some cases, wish to comprise in the composition pH when micro-encapsulated acid contacts with blade to reduce spray solution.

Other optional members of the present composition comprise the reagent that changes color, smell, viscosity, gelling, freezing point, stability or structure.

Also can comprise except that the amines of formula (I) or one or more surfactants its amphoteric salt in the composition of expection.Many surfactants can be used for the prescription of xenobiotics and can easily be selected from classic, as McCutcheon ' s Emulsifiers andDetergents, 1997 editions, MC Publishing Company, or Handbook ofInustrial Surfactants, the 2nd edition, Gower (1997).

To the type of spendable surfactant or chemical classification without limits.As the case may be, nonionic, anion, anion and amphoteric type, or not only one type composition all can use.

This paper can with many surfactants have such chemical constitution, promptly comprise one or more by single C _2-4Alkylene oxide unit or C _2-4The part that the polymerization of alkylene oxide unit or copolymerization chain constitute.This surfactant is called as polyoxyalkylene surfactants and comprises nonionic, anion, cation and amphoteric type.The polyoxyalkylene surfactants of available present contemplated composition contains has an appointment 2 to about 100 C _2-4Alkylene oxide unit.In preferred polyoxyalkylene surfactants, alkylene oxide unit forms the oxirane and the expoxy propane chain of one or more ethylene oxide chain or copolymerization, and every alkylene oxide unit chain all has terminal hydrogen or C _1-4Alkyl or C _2-4The acyl group end-blocking.

The hydrophobic part that can be used for the surfactant of the present composition is alkyl substantially, and hydrophobic part wherein generally is C _8-24, preferred C _12-18Alkyl, thiazolinyl, alkaryl, alkanoyl or enoyl-.These chains can be linearity or branch.As selection, hydrophobic part can contain silicon atom, for example with the form of siloxane group as seven methyl trisiloxanes groups, or fluorine atom, for example partially fluorinated alkyl or perfluoroalkyl chain.

In non-ionic surface active agent, that particularly preferred type comprises is polyxyethylated, thiazolinyl or alkyl aryl ether, as polyoxyethylene uncle or secondary alcohol, alkyl phenol or acetylenediol; Polyxyethylated or alkenyl esters is as ethoxylated fatty acid; Sorbitan Arrcostab, no matter whether ethoxylation; The glyceryl Arrcostab; Sucrose ester; And alkyl poly glucoside.The representative instantiation of this anion surfactant comprises polyoxyethylene (9) nonyl phenol, the Neodol of Shell ^TM25-7 (polyoxyethylene (7) C _12-15Linear primary alcohol), the Plurafac of BASF ^TMA-38 (polyoxyethylene (27) C _16-18Linear primary alcohol), the Tergitol of Union Carbide ^TM15-S-9 (polyoxyethylene (9) C _12-15Secondary alcohol), the Tween of ICI ^TM20 (polyoxyethylene (20) sorbitan monolaurates), the Surfynol of Air Products ^TMThe Agrimul of 465 (polyoxyethylene (10) 2,4,7,9-tetramethyl-5-decine-4,7-glycol) and Henkel ^TMPG-2069 (C _9-11Alkyl poly glucoside).

When comprising non-ionic surface active agent, non-ionic surface active agent preferably exists with amount of auxiliary, promptly is enough to provide the amount of the xenobiotics biopotency that significantly improves than the composition that lacks this surfactant." significantly improve " herein and be illustrated in the comparison arranged side by side, the biopotency difference that support contains the composition of non-ionic surface active agent is that significantly for example the weeds scientist is under the situation of weed killer herbicide at xenobiotics for the knack person of the concrete classification association area of the xenobiotics that is applied.

If comprise non-ionic surface active agent, contain one or more non-ionic surface active agents in the preferred composition, the gross weight of this surfactant is about 1: 10 to about 10: 1 with the ratio of the weight of the anion xenobiotics of representing with acid equivalent, preferred about 1: 3 to 3: 1, also can use although under special situation, find quantity bigger or still less.

In anion surfactant, particularly preferred type comprises fatty acid; Benzene sulfonate and diphenyl ether disulfonate that alkyl replaces; Napsylate; Acyl group isethionic acid ester, sarcosinate, esters of sulfosuccinic acids, half esters of sulfosuccinic acids, sulfo-succinamide ester and taurine ester; Alkane and-the alkene sulfonic acid ester; The sulphate of oil ﹠ fat acid esters and sulfonate; The sulphate of alcohol, alkyl phenol, the pure and mild polyoxyethylene alkylphenol of polyoxyethylene, sulfonate and phosphate list-and diester; With the carboxylate of polyoxyethylene alcohol with regard to polyoxyethylene alkylphenol.These compounds can its acid or for example form use of sodium salt, sylvite or ammonium salt of salt.

In a specific embodiments of the present invention, provide a kind of and be used to be administered to plant leaf surface to cause the plant treatment compositions of biological respinse, said composition comprises water, dissolves or disperseed the amines of a kind of anion xenobiotics and one or more formulas (I) in the water

R wherein ¹Be alkyl, preferred linear alkyl chain contains 6 to about 22 carbon atoms, and the R of all existence ¹At least 30% of group contains has an appointment 14 to about 22 carbon atoms, R ²And R ³Be C independently _1-5Alkyl; The amount that wherein contains xenobiotics in the composition should be enough to when with about 10 consumptions to about 1000 liters of per hectares (l/ha) said composition being administered to plant leaf surface, causes biological respinse; Wherein the mol ratio of the formula that contains in the composition (I) amines and xenobiotics is about 0.01: 1 to about 0.8: 1, preferably approximately 0.05: 1 to about 0.8: 1, and more preferably from about 0.1 to about 0.5: 1; Said composition also contains a kind of anion surfactant, and the mol ratio of itself and formula (I) amines is about 0.1: 1 to about 10: 1, and preferred about 0.5: 1 to about 2: 1, most preferably from about 0.8: 1 to about 1.2: 1.

The preferred anionic surfactants surfactant that can be used for this embodiment of the present invention is selected from the above listed hydrophobic C that contains _8-24, preferred C _12-18The type of alkyl, thiazolinyl, acyl group or alkylaryl group.In containing the anion surfactant of polyoxyethylene chain, this chain preferably contains 1 to about 60 ethylene oxide units.

In cationic surfactant, particularly preferred type comprises polyoxyethylene trialkylamine or alkenyl amine such as ethoxylated fatty amine, quaternary surfactant and polyoxyethylene alkyl ether amine.The representative instantiation of this cationic surfactant comprises polyoxyethylene (5) coconut amine, polyoxyethylene (15) beef tallow amine, distearyl alkyl dimethyl ammonium chloride, N-dodecylpyridine chloride thing and polyoxyethylene (8) oxygen ethene trimethyl ammonium chloride.Particularly preferred polyoxyethylene alkyl ether amine is to be disclosed among the international publication number WO96/32839 those.

The cationic quaternary ammonium surfactant of many different structures is in the composition that can be used in combination with glyphosate and other xenobioticses and that can be used for this paper expection known in the art; This quaternary surfactant has general formula (VII):

Wherein Z-be suitable anion such as chloride, bromide, iodide, acetate, salicylate, sulphate or phosphate; K and m are integers, so that the negative electrical charge on positive charge on the cation and the anion contends with; R ^a, R ^b, R ^cAnd R ^dSelection comprise following groups without limitation:

(i) R ^aBe benzyl or C _8-24, preferred C _12-18Alkyl or alkenyl, R ^b, R ^cAnd R ^dBe C independently _1-4Alkyl, preferable methyl;

(ii) R ^aAnd R ^bBe C independently _8-24, preferred C _12-18Alkyl or alkenyl, R ^cAnd R ^dBe C independently _1-4Alkyl, preferable methyl;

(iii) R ^aBe C _8-24, preferred C _12-18Alkyl or alkenyl; R ^bBe to contain about 2 to about 100 C _2-4The polyoxyalkylene chain of alkylene oxide unit optimization ethylene oxide unit, R ^cAnd R ^dBe C independently _1-4Alkyl, preferable methyl;

(iv) R ^aBe C _8-24, preferred C _12-18Alkyl or alkenyl; R ^bAnd R ^cBe to contain about altogether 2 to about 100 C _2-4The polyoxyalkylene chain of alkylene oxide unit optimization ethylene oxide unit, and R ^dGround is C _1-4Alkyl, preferable methyl; Or

(v) R ^aBe to contain about 2 to about 100 C _2-4The polyoxyalkylene chain of alkylene oxide unit, wherein C _3-4The preferred propylene oxide units of alkylene oxide unit is preponderated R ^b, R ^cAnd R ^dBe C independently _1-4Alkyl, preferable methyl or ethyl.

Particularly preferred this type quaternary surfactant is disclosed in U.S.5464807.

In the preferred embodiment of the invention, contain amphoteric quaternary ammonium compound or its mixture of formula (VIII):

R wherein ^eBe to contain about 6 alkyl or haloalkyls to about 22 carbon atoms; W and Y are O or NH independently; A and b are 0 or 1 independently, but one of them is 1 at least; X is CO, SO or SO ₂N is 2 to 4; R ^f, R ^gAnd R ^hBe C independently _1-4Alkyl; The implication cotype (VII) of k, m and Z-.R in a specific embodiments ^eBe to contain about 12 alkyl to about 18 carbon atoms.R ^eAlso can be fluoridized.In a specific embodiments, R ^eBe perfluoro, preferably contain about 6 to about 12 carbon atoms.In an especially preferred embodiment, R ^eBe the saturated perfluoroalkyl that contains about 12 carbon atoms, X is CO or SO ₂, Y is NH, and a is 0, and b is 1, and n is 3, R ^f, R ^gAnd R ^hBe methyl, k and m are 1, Z ^-Be chloride, bromide or iodide anion.

The sulfonamido compound of special preferred formula (VIII), promptly wherein X is SO ₂, Y is NH, and a is 0, and b is 1.Suitable example comprises 3-(((17 fluoro octyl group) sulfonyl) amino)-N, N, N-trimethyl-1-propaminium iodide, the Fluorad of available 3M company ^TMFC-135 and corresponding chlorinated thing.It is believed that the Fluorad of 3M company ^TMFC-754 contains the corresponding chlorinated thing.

When comprising the amphoteric quaternary ammonium compound of formula (VIII), this compound preferably exists with the auxiliary agent content of non-ionic surface active agent definition as mentioned.If comprise the amphoteric quaternary ammonium compound of formula (VIII), the gross weight of contained this compound is about 1: 100 to about 1: 3 with the ratio of the weight of the anion xenobiotics of representing with acid equivalent in the preferred composition.The suitable concentration of formula (VIII) compound in plant treatment compositions is extremely about 1 weight % of about 0.001 weight %, and the suitable concentration in liquid concentration plant of the present invention is that about 0.01 weight % is to about 10 weight %.

Yet the another kind of figuration material that can be used for the present composition is an oil, as the triglyceride of animal, plant or synthetic fatty acid of originating, paraffin, polysiloxanes, or its fatty acid or ester or acid amides.The mixture of described oil or oil exists with aforesaid auxiliary agent content.The example of suitable oil comprises the triglyceride of coconut oils, as the product Miglyol of Hls ^TM812, corn oil, olive oil, C _12-15Alkyl benzoate, eicosapentaenoic acid and DHA and Arrcostab thereof and triglyceride and sad triglyceride.Oil can be fractionation or not fractionation.Thereby fractionation can be removed some fatty acid chain length and be changed fusing point.

In a specific embodiments of the present invention, contain one or more oil, every kind of chemical constitution that all has corresponding to formula (IX):

R ¹⁴-CO-Y-R ¹⁵????(IX)

R wherein ¹⁴Be to contain 5 the alkyl of having an appointment, R to about 21 carbon atoms ¹⁵Be to contain 1 alkyl, R to about 14 carbon atoms ¹⁴And R ¹⁵The total number of carbon atoms be about 10 to about 27, Y is O or NH.R ¹⁴And R ¹⁵Preferred linear alkyl chain.R ¹⁴Preferably contain about 11 to about 21 carbon atoms and preferably derive from natural saturated or unsaturated fatty acid.R ¹⁵Preferably have 1 alkyl to about 6 carbon atoms.Therefore particularly preferred formula (IX) oil is the C of fatty acid _1-6Arrcostab or C _1-6Alkylamide.The more preferably weight meter of contained all formulas (IX) compound in composition, approximately 40-100%R ¹⁴Be saturated.

In some preferred embodiments, comprise such oil, i.e. C _12-18The C of fatty acid _1-4Arrcostab, more preferably C _12-18The C of saturated fatty acid _1-4Arrcostab.Example comprises methyl oleate, ethyl oleate, isopropyl myristate, isopropyl palmitate and butyl stearate.Preferred especially butyl stearate.

When containing one or more formulas (IX) oily, the gross weight of preferred described oil is about 1: 100 to about 10: 1 with the ratio of the weight of the anion xenobiotics of representing with acid equivalent, preferred about 1: 100 to 1: 1, most preferably about 1: 10 to about 1: 3, also can use although under special situation, find quantity bigger or still less.

The suitable concentration of formula (IX) compound in plant treatment compositions is extremely about 1 weight % of about 0.001 weight %, and the suitable concentration in liquid concentration plant of the present invention is that about 0.01 weight % is to about 10 weight %.

If oil-containing in the present composition, the anionic compound of available formula (I) or its amphoteric salt emulsification should oil.If desired, can comprise the emulsifier of extra surfactant as described oil.It is believed that oil particularly formula (IX) the oil existence in composition can further enhancing xenobiotics infiltrate or see through plant epidermis, perhaps this be owing to given composition more lipophilicitys.

The influence that comprises suitable oil in the present composition normally increases supramolecular aggregation formation and steeps rise micella or latex particle.In this composition, the mean size of supramolecular aggregation in the scope of above-mentioned not oil compositions or bigger, for example about at the most 1000nm.

It is the compound that comprises polyoxyethylene chain that one class assistant agent compound of the biopotency of surprising enhancing can be provided when having found in being contained in the present composition, and described polyoxyethylene chain contains has an appointment 2 to about 100 ethylene oxide units.Described compound can contain not only this polyoxyethylene chain.Described compound can be the surfactant that also contains a hydrophobic part, but may not be surfactant.For example, the polyethylene glycol of mean molecule quantity about 100 to about 4000 is exactly this compound.Many above-mentioned polyoxyethylene surfactant also can satisfy the requirement of this compound.Illustrative example is polyoxyethylene (15) beef tallow amine and polyoxyethylene (27) C _16-18Alcohol.

If contain the polyoxyethylene compound of describing just now, then the weight ratio of contained this compound and anion xenobiotics is about 1: 10 to about 10: 1 in the plant treatment compositions, preferred about 1: 3 to about 3: 1.Usually this is corresponding to about 0.005% to about 5%, and preferably approximately 0.05% to about weight concentration of 1%, most preferably about 0.1% to about 0.5%.In liquid concentrating composition, if contain polyoxyethylene compound, then the preferred weight concentration of this compound is about 5% to about 20%.Find under special circumstances to use greater or lesser quantity.

Therefore in a specific embodiments of the present invention, provide a kind of and be used to be administered to plant leaf surface to cause the plant treatment compositions of biological respinse, said composition comprises water, dissolves or disperseed the amines of anion xenobiotics and one or more formulas (I) in the water

R wherein ¹Be alkyl, preferred linear alkyl chain contains 6 to about 22 carbon atoms, and the R of all existence ¹At least 30% of group contains has an appointment 14 to about 22 carbon atoms, R ²And R ³Be C independently _1-5Alkyl; The amount that wherein contains xenobiotics in the composition should be enough to when with about 10 consumptions to about 1000 liters of per hectares (l/ha) said composition being administered to plant leaf surface, causes biological respinse; Wherein the mol ratio of the formula that contains in the composition (I) amines and xenobiotics is about 0.01: 1 to about 0.8: 1, preferably approximately 0.05: 1 to about 0.8: 1, and more preferably from about 0.1 to about 0.5: 1; Said composition also contains a kind of assistant agent compound, the molecular structure of this compound comprises and contains about 2 polyoxyethylene chains to about 100 ethylene oxide units, the mol ratio of this compound and xenobiotics is about 1: 10 to about 10: 1, preferred about 1: 3 to about 3: 1.

Concentrate composition

Although the above-mentioned plant treatment compositions with respect to above-mentioned arbitrary embodiment can original position be mixed with dilute aqueous or dispersion before being administered to plant leaf surface, the preferred embodiment of the invention is a kind of concentrate composition of stable storing.When in the water that is dissolved or dispersed in Sq or during dilute with water, concentrate composition of the present invention forms above-mentioned plant treatment compositions.Therefore the components in proportions in addition that dewaters that is the plant treatment compositions definition of this paper is equally applicable to concentrate composition.Generally when the preparation plant treatment compositions, 1 weight portion concentrate composition is added in about 9-99 weight parts water; Yet can use the water of more or less amount under special circumstances.

Concentrated plant of the present invention can be solid or liquid.The preparation type of the anion xenobiotics of foliage applying that generally is applicable to known in the art can be used for the present invention.These formulations unrestrictedly comprise concentrated aqueous solution and dispersion, emulsion (comprising oil-in-water, Water-In-Oil and W/O/W type), microemulsion, suspending concentrate, emulsible concentrate, suspension emulsion, wetting powder, water solube powder and granule, water-dispersible pulvis and granule etc.

Solid concentrate composition of the present invention contains total at least about 5 weight % and about at the most 75% or the higher xenobiotics of representing with acid equivalent as water-soluble or water-dispersible granular material agent.The preferred content of xenobiotics in solid concentrate composition is about 25-75 weight %, more preferably about 50-75 weight %a.e..Solid concentrate composition is called as " doing " preparation sometimes; This should not be considered to imply said composition is not moisture or other liquid fully, only represents that they touch up to do.

Liquid concentrating composition of the present invention as the aqueous solution or dispersion, contains total at least about 5 weight % and about at the most 50% or the higher xenobiotics of representing with acid equivalent.The preferred content of xenobiotics in solid concentrate composition is about 20-45 weight %, more preferably about 30-45 weight %a.e..

The preparation method of the present composition

Concentrate composition of the present invention can be by following conventional steps preparation; Yet the present invention is not limited to the composition by these step preparations.

In the appropriate method of preparation liquid concentrating composition, the first step is a neutralization procedure.This step is included in liquid medium, in the preferred water-bearing media, by stirring amines with one or more formulas (I) the first molal quantity X that neutralizes ¹The anion xenobiotics, contain the fluid composition of one or more amphoteric salts of xenobiotics with preparation, be in the example of glyphosate at an xenobiotics of neutralization procedure, with the glyphosate (GH of first molal quantity ₂) add in the water with the amines of formula (I), addition is about 1-2 mole amines/mole glyphosate, with preparation monovalent salt [GH ^-] [A ⁺], divalent salts [G ^2-] [A ⁺] ₂Or the mixture of this monovalent salt and divalent salts, wherein A ⁺Be to derive from the protonated cation of this amines.The relative mol ratio of monovalent salt and divalent salts is the function of the amines quantity/mole glyphosate of interpolation.

Neutralization procedure also can comprise by stirring introduces the second molal quantity X in fluid composition ²Xenobiotics, this part xenobiotics is except by the first molal quantity X ¹The form of one or more salt beyond the amphoteric salt that forms.At an xenobiotics is in the example of glyphosate, adds monovalent salt [GH ^-] [B ⁺], divalent salts [G ^2-] [B ⁺] ₂Or the second molal quantity X of the form of mixtures of this monovalent salt and divalent salts ²Glyphosate, wherein B+ derives from except being used to the first molal quantity X that neutralizes ¹The cation of the alkali beyond the amines of the formula of glyphosate (I).

Because A ⁺And B ⁺The quantity not sufficient of the alkali of cation source can select to exist the 3rd molal quantity X with all xenobioticses that exist that neutralize in the neutralization procedure process ²Xenobiotics, but this material is not neutralized.

The salt of the xenobiotics of second molal quantity can shift to an earlier date independent preparation, or in liquid medium by being stirred in original position with the second molal quantity manufacturing that neutralizes of one or more alkali except that the amines of first molal quantity that is used to neutralize.Which kind of situation no matter, the introducing of this salt all can before the xenobiotics of neutralization first molal quantity, among or take place afterwards.

Neutralization procedure carries out with stirring, and magnetic stirring apparatus is for example used in preferred gentle stirring.In a preferred embodiment, neutralization procedure carries out under the temperature of the fusing point that is higher than used formula (I) amines.Usually the temperature of liquid medium is about 50-100 ℃ in the neutralization procedure.

In suitable method, second step was a regulating step.This step comprises that continuing the agitated liquid composition is scattered in the liquid medium until the supramolecular aggregation colloidal state that contains the xenobiotics amphoteric salt, and the amphoteric salt of described xenobiotics is by forming with xenobiotics in the amines of using formula (I).Stir, preferred gentle agitation can provide by the same sampling device that is used to stir in neutralization procedure.In regulating step preferred keep to neutralization procedure in the similar high temperature that provides.Regulating step sustainable a few minutes were to several hours and cause the stable colloidal dispersion of spontaneous formation supramolecular aggregation, generally were the forms with above-mentioned micella and bigger aggregation.

Composition except that the salt of xenobiotics can be before neutralization procedure, in or before back and the regulating step, in or after be dissolved or dispersed in the liquid medium.The best interpolation order of any composition can be determined at an easy rate by normal experiment.

The product of method mentioned above is a liquid concentrating composition, and the plant treatment compositions of first embodiment of the invention can be provided when it is diluted in water.

The replacement method describes as xenobiotics with reference to glyphosate.In the first step, preparation comprises first concentrated aqueous solution of the low-molecular-weight counter cation salt of glyphosate.For example, by in water-bearing media with in suitable alkali such as sodium hydroxide ammoniacal liquor or the isopropylamine and glyphosate prepare first concentrated aqueous solution.In second step, preparation comprises second concentrated aqueous solution or the dispersion of the acid salt of formula (I) amines.For example, by in water-bearing media, preparing second concentrated aqueous solution or dispersion with suitable sour example hydrochloric acid sulfuric acid or acetate neutralized amine compound.In the 3rd step, mixed first concentrated aqueous solution and second concentrated aqueous solution or dispersion are to form liquid concentrating composition of the present invention.

The product of this replacement method is a liquid concentrating composition, according to the result of the test of composition mentioned above, can provide the plant treatment compositions of the present invention first or second embodiment when it is diluted in water.

The method for preparing liquid concentrating composition of the present invention comprises anion xenobiotics or the mixture of its salt or this anion xenobiotics and salt thereof and the amines of one or more formula (I) of the first step with solid particulate form, and and the mixed together wet-mixing thing that forms of the water of capacity, this wet-mixing thing denseness should be applicable to further step hereinafter described.In this mixed step, can comprise other compositions.The amines of formula (I) and xenobiotics are mixed to calculate the relative quantity that can be provided at expection mol ratio in the solid concentrate composition.Under lower mol ratio, for example about at the most 0.3: 1, the wet-mixing thing of formation was suitable for further processing, and need not the existence of any solid inert carrier; But under higher mol ratio, may find to comprise solid inert carrier so that obtain the wet-mixing thing of expection denseness.Suitable solid inert carrier is well known by persons skilled in the art; Example comprises finely divided silica dioxide granule, mineral salt such as ammonium sulfate etc.The appropriate amount of each composition can be determined by routine test by those skilled in the art in the mixed step.

This method comprises that also second step formed wet bonded particulate and dry this particle of the 3rd step with this wet-mixing thing granulation.Any method of granulating of the water-soluble or water-dispersible granular material of suitable preparation xenobiotics known in the art all can use; Method for optimizing is dish granulation and extruding pelletization.The extruding pelletization method that is disclosed in UK Patent Application 1433882 is a kind of illustrative method, can be used for preparing particulate composition of the present invention.Can use any drying means of the water-soluble or water-dispersible granular material of suitable preparation xenobiotics known in the art; Method for optimizing is a fluid-bed drying.

Use contemplated composition to blade

Xenobiotics is administered on the plant with the amount that is enough to produce predictive role.These rate of application generally are expressed as the amount that per unit is handled the xenobiotics that appears on the market, and for example restrain per hectare (g/ha)." predictive role " is according to investigating, develop, sell and using the people's of concrete kind xenobiotics standard and practice to change.For example under the situation of weed killer herbicide, generally use the amount of application of the per unit area that can produce plant variety control rate unanimity and reliable at least 85% to determine that commerce is efficient, described control rate is to measure by growth reduction or lethality.

Herbicide action is one of biological agent that can strengthen by the present invention." herbicide action " used herein refers to any visible plant growing control degree, and comprise one or more following effects: kill (1), and (2) suppress growth, and breeding or propagation and (3) are removed, destroyed, or reduce appearance and the activity of plant on the contrary.

For concrete xenobiotics is that the biological effectively selection of rate of application is in common Agricultural Scientist's skill.Those skilled in the art will appreciate that equally the concrete xenobiotics of special planting conditions, weather and growth conditions and selection and composition thereof can influence the degree of putting into practice biopotency obtained when of the present invention.The useful rate of application of used xenobiotics depends on above-mentioned all conditions.With respect to the application that the inventive method is used for glyphosate herbicidal, about the suitable known more information of rate of application.Surpass that vicennial glyphosate uses and the open research that relates to this application provides bulk information, it is the effective glyphosate rate of application of weeding under special environmental conditions at special vegetative stage that the control of weeds practitioner can select for particular strain in view of the above.

The Herbicidal combinations of glyphosate or derivatives thereof is used to prevent and treat worldwide various plants.Glyphosate composition of the present invention can be administered on the plant by herbicidally effective amount, and can unrestrictedly effectively prevent and treat one or more plants that belong to following one or more genus: abutilon, Amaranthus, artemisia, milkweed, Avena, carpetweed belongs to, Borreria, Brachiaria, rape belongs to, Brome, Chenopodium, Cirsium, dayflower belongs to, and japanese bearbind belongs to, Cynodon, Cyperus, knotgrass, Echinochloa, eleusine indica belongs to, and wild wheat belongs to, Equisetum, Erodium, Helianthus, cogon, sweet potato genus, summer cypress, Lolium, mallow, Oryza, half Ying's Panicum, Panicum, Paspalum, ◆ grass belongs to, and reed belongs to, Polygonum, Portulaca, Cyclosorus, Pueraria lobota is with belonging to rubus, Salsola, setaria, chrysanthemum harvest spp, mustard belongs to, sorghum, Triticum, typha, chaste tree Macroptilium, Xanthium and Zea.

The annual broadleaf weed of the particular importance that glyphosate composition is suitable for illustrates without limitation by following weeds: piemarker (Abutilon theophrasti), Amaranthus (Amaranthus spp.), the button grass belongs to (Borreria spp.), rape (oilseedrape), canola, leaf mustard etc. (Brassicas), dayflower belongs to (Commelina spp.), mang ox seedling belongs to (Erodium spp.), Helianthus (Helianthus spp.), sweet potato genus (Ipomoea spp.), summer cypress (Kochia scoparia), mallow (Malva spp.), corn-bind, knotweed etc. (Polygonum), Portulaca (Portulaca spp.), seed artemisia (Salsolaspp.), chrysanthemum harvest spp (Sida spp.), wild field mustard (Sinapis arvensis) and U.S. Siberian cocklebur (Xanthium).

The annual grass of the particular importance that glyphosate composition is suitable for illustrates without limitation by following weeds: wild oat (Avena fatua), carpetweed belongs to (Axonopusspp.), downy brome (Bromus tectorum), knotgrass (Digitaria spp.), barnyard grass (Echinochloa crus-galli), eleusine indica (Eleusine indica), Italian ryegrass (Lolium multiflorum), rice (Oryza sativa), half Ying's Panicum (Ottochloa nodosa), Bahia grass (Paspalum notatum), ◆ grass belongs to (Phalaris spp.), setaria (Setaria spp.), wheat (Triticumaestivum) and corn (Zea mays).

The perennial broadleaf weed of the particular importance that glyphosate composition is suitable for illustrates without limitation by following weeds: artemisia (Artemisia spp.), milkweed (Asclepiasspp.), Canada Ji (Cirsium arvense), field bindweed (Convolvulus arvensis) and Pueraria lobota belong to (Pueraria spp.).

The perennial grassy weed of the particular importance that glyphosate composition is suitable for illustrates without limitation by following weeds: Brachiaria (Brachiaria spp.), Bermuda grass (Cynodondactylon), earth almona (Cyperus esculentus), nutgrass flatsedge (C.rotundus), couchgrass (Elymus repens), cogongrass (Imperata cylindrica), perennial ryegrass (Loliumperenne), big broomcorn millet (Panicum maximum), hairy flowered paspalum (Paspalumdilatatum), reed belongs to (Phragmites spp.), Johnson grass (Sorghumhalepense) and typha (Typha spp.).

Other perennial kinds of the particular importance that glyphosate composition is suitable for illustrate without limitation by following weeds: Equisetum (Equisetum spp.), fiddlehead (Pteridiumaquilinum), rubus (Rubus spp.) and chaste tree beans (Ulex europaeus).

Therefore, glyphosate composition of the present invention and can be used for above-mentioned any kind with the method for described compositions-treated plant.In a special expection method, the plant treatment compositions that the present invention includes one or more salt form glyphosates is applied on the blade of crop, described crop is to convert glyphosate tolerant in the heredity, is administered on the grass cutting blade simultaneously or is grown near the described crop the undesired plant.This method energy controlling weeds or unwelcome plant make crop preserve from substantially simultaneously.The crop that is transformed into glyphosate tolerant from heredity comprises that its seed has Roundup Ready by the Monsanto sale or through the Monsanto permission ^Those crops of trade mark.These crops comprise respectively grow cotton, soybean, canola and corn.

Plant treatment compositions is administered on the blade preferably finishes, use any usual manner of spraying liquid, as nozzle or spinning disc atomizer by spraying.Composition of the present invention can be used in the accurate farming technique, wherein according to variable as the plant variety that exists, plant growing stage, soil moisture content situation etc., operative installations is to change the amount that xenobiotics is administered to the field different piece.In an embodiment of described technology, can use global positioning system to operate the different piece that the composition of desired amount is administered to the field with sprayer unit.

The preferred fully dilution of plant treatment compositions is to be convenient to the agricultural spray device sprinkling with standard.Be applicable to rate of application of the present invention according to this change of many factors, described factor comprises the type of active component and concentration and the plant variety that relates to thereof.By spraying the effective dose that Aquo-composition is administered to the blade scope is about 25-1000 liter/hectare (l/ha), preferably approximately 50-300l/ha.

Be used for causing plant or be present in the plant or on pathogene, parasite or consumer organism in the bioactive expection method of expection also be included in plant treatment compositions of the present invention be administered to before the step on the plant leaf blade, with concentrate composition dilution provided herein, be dissolved or dispersed in the water of proper volume to form the step of plant treatment compositions.

Embodiment

The following example only is to be used for illustration purpose and to be not to be intended to limit the scope of the invention.Embodiment can understand some difference of the present invention and advantage and effect better.

Embodiment 1

1.2g (is equaled 6.1mmolGH ₂) the wet pie glyphosate that contains 86.5 weight %a.e. glyphosates adds in the 30ml flask.Add the 1.3gN-coconut alkyl-N that is equivalent to 6.1mmol (supposing 12 carbon atoms of coconut alkyl average chain length) as calculated, the N-dimethyl amine (Noram of CECA S.A. then ^TMDMC D), the mol ratio that obtains amine and glyphosate a.e. is 1: 1.Then add the water (through ion exchange with by 0.2 μ m filter) of 20ml deionization,, provide aqueous medium with glyphosate in the N-dimethyl amine for N-coconut alkyl-N.

Flask clogged and is placed in 60 ℃ of water-baths 2 hours.It is thoroughly mixed to guarantee to apply magnetic agitation.

Obtain the stable colloidal dispersion of low viscosity and pH about 4.The feature of this colloidal dispersion is determined by following method.

The stability of colloidal dispersion is determined by observing.If the preparation flask under stirring condition not under room temperature storage do not occur being separated in 48 hours, then this colloidal dispersion is thought stable concerning present embodiment.

CMC is the Wilhemy method by flat band method or common name, uses Kruss K12 auto-tensiometer to determine 25 ℃ of surface tension of measuring each concentration range.Because said composition is diluted, initial surface tension force is uninfluenced substantially.After reaching CMC, further dilution can cause surface tension to increase progressively, final surface tension near pure water.If on the curve map with respect to concentration rendered surface tension force on logarithmic coordinates, the curve map that produces has sharp-pointed turnover at a special some place, be subjected to the influence of concentration at this following table surface tension, put the influence that above surface tension was not subjected to or was subjected to hardly concentration at this.Concentration at this break is equivalent to CMC.

The size of the supramolecular aggregation bigger than simple micella is to measure by using transmission electron microscope (TEM) to observe with the negative staining technology.The colouring agent that uses is tungstosilicic acid sodium Na ₄(Si (W ₃O ₁₀) ₄) .20H ₂O.Show in the composition of embodiment 1 that the transmission electron micrograph greater than the supramolecular aggregation of about 20nm is positioned at Fig. 1.

Embodiment 1 the results are shown in the following table 1.

Embodiment 2

Method according to embodiment 1 is carried out, and is the Noram of CECA S.A. except used amines ^TMDMSH D, this is the alkyl dimethyl amine that is come by the h-tallow preparation, its main component is N-stearoyl-N, the N-dimethyl amine.The addition of amine is 1.812g.Embodiment 2 the results are shown in following table 1.

Embodiment 3

Method according to embodiment 1 is carried out, except using the N-coconut alkyl-N of 50: 50 mol ratios, N-dimethyl amine (Noram ^TMDMC D) and N-stearoyl-N, N-dimethyl amine (Noram ^TMDMSH D).The adding total amount of amine is 1.55g (0.65g Noram ^TMDMC D and 0.9g Noram ^TMDMSH D).Embodiment 3 the results are shown in following table 1.

Embodiment 4

Method according to embodiment 1 is carried out, and except N-coconut alkyl-N, the addition of N-dimethyl amine is 2.6g, so that 2: 1 amine and glyphosate mol ratio to be provided.Embodiment 4 the results are shown in following table 1.

Table 1: the result of embodiment 1-4

Embodiment	Amines ¹	Mol ratio ²	Outward appearance	CMC(μM)	Surface tension (mN/m) at CMC
Embodiment	Amines ¹	Mol ratio ²	Outward appearance	CMC(μM)	Surface tension (mN/m) at CMC	????1	Coconut-N (Me) ₂	???1∶1	Limpid	???37	????26.5
????2	C ₁₈-N(Me) ₂	???1∶1	Limpid to muddy	???31	????30.7	????1	Coconut-N (Me) ₂	???1∶1	Limpid	???37	????26.5
????2	C ₁₈-N(Me) ₂	???1∶1	Limpid to muddy	???31	????30.7	????3	Coconut-N (Me) ₂+C ₁₈-N(Me) ₂	???1∶1	Limpid	Do not measure	Do not measure
????4	Coconut-N (Me) ₂	???2∶1	Limpid	???35	????22.5	????3	Coconut-N (Me) ₂+C ₁₈-N(Me) ₂	???1∶1	Limpid	Do not measure	Do not measure

¹The amines of formula (I); But the abbreviation reference example of amines is understood.

²The amines of formula (I) and the mol ratio of glyphosate a.e..

Embodiment 5

1.2g (is equaled 6.1mmolGH ₂) the wet pie glyphosate that contains 86.5 weight %a.e. glyphosates adds in the 30ml flask.Add 0.65gN-coconut alkyl-N then, the N-dimethyl amine (Noram of CECA S.A. ^TMDMC D), this consumption is that the mol ratio so that amine and glyphosate a.e. to be provided as calculated is 0.5: 1.Then add the water (through ion exchange with by 0.2 μ m filter) of 20ml deionization,, provide aqueous medium with glyphosate in the N-dimethyl amine for N-coconut alkyl-N.

Flask clogged and is placed in 60 ℃ of water-baths 2 hours.It is thoroughly mixed to guarantee to apply magnetic agitation.Continue to stir then and add 0.822g three hexyl amines, this consumption be as calculated so that itself and N-coconut alkyl-N are provided, the mol ratio of the total alkali content of N-dimethyl amine and glyphosate a.e. is 1: 1.In water-bath, continue again to stir 30 minutes.

Obtain the stable colloidal dispersion of low viscosity and pH about 4.

Embodiment 6

Method according to embodiment 5 is carried out, except the sodium hydroxide solution with 3.05ml 1M replaces three hexyl amines.Obtain the stable colloidal dispersion of low viscosity and pH about 4.

Embodiment 7

With 2.52gN-coconut alkyl-N, the N-dimethyl amine (Noram of CECA S.A. ^TMDMCD) with the 0.888g triglyceride fat acid esters oil (Miglyol of H ü ls ^TM817) join together in the 30ml flask.Flask is clogged and be placed on 60 ℃ of stirred in water bath until N-coconut alkyl-N, and the N-dimethyl amine is dissolved in the oil.Add 2.35g (12mmolGH then ₂) wet pie contain the glyphosate of 86.5 weight %a.e. glyphosates.The water (through ion exchange with by 0.2 μ m filter) that then adds the 20ml deionization.

Obtain the stable muddy emulsion of low viscosity and pH about 4.

The particle diameter of the emulsion compositions of embodiment 7 distributes and is to use Coulter LS230 device to measure by optical diffraction.The diameter of the oil phase particle of this emulsion (bubble rise micella) is 300-3000nm, and as shown in Figure 3, volume mean diameter is about 780nm.

Embodiment 8

With 13.8gN-octyl group-N, the N-dimethyl amine, 12.0g glyphosate (96 weight % by analysis) and 214g distilled water join in the screw-topped pipe-type bottles of 500ml.Therefore the mass fraction of the glyphosate that adds is 50 gram/kilograms (g/Kg).Each mixture of ingredients 50 ℃ of magnetic agitation 5 hours, is obtained limpid supramolecular aggregation colloidal dispersion.This dispersion is cooled to room temperature.Size (passing through dynamic light scattering) at pH and the supramolecular aggregation of after glyphosate concentration is 5g a.e./Kg, measuring preparation with this dispersion of distilled water diluting.The supramolecular aggregation of 50g a.e./Kg at room temperature do not had leave standstill its situation that is separated that detected in 48 hours under the stirring condition.Embodiment 8 the results are shown in following table 2.

Embodiment 9

Method according to embodiment 8 is carried out, except amines is N-coconut alkyl-N of 17.3g, and N-dimethyl amine (Noram ^TMDMC D), the addition of glyphosate is that the addition of 12.0g and distilled water is 211g.Embodiment 9 the results are shown in following table 2.

Embodiment 10

Method according to embodiment 8 is carried out, except amines is N-tallow alkyl-N of 33.0g, and N-dimethyl amine (Noram ^TMDMS D), the addition of glyphosate is that the addition of 12.0g and distilled water is 195g.Embodiment 10 the results are shown in following table 2.

Table 2: the result of embodiment 8-10

Embodiment	Amines ¹	Mol ratio ²	Outward appearance	Be separated	The average grain diameter of aggregation (nm)
Embodiment	Amines ¹	Mol ratio ²	Outward appearance	Be separated	The average grain diameter of aggregation (nm)	??8	??C ₈-N(Me) ₂	??1.29∶1	Limpid	Do not have	Do not measure
??9	Coconut-N (Me) ₂	??1.19∶1	Limpid	Do not have	????4.4	??8	??C ₈-N(Me) ₂	??1.29∶1	Limpid	Do not have	Do not measure
??9	Coconut-N (Me) ₂	??1.19∶1	Limpid	Do not have	????4.4	??10	Butter-N (Me) ₂	??1.64∶1	Limpid	Do not have	????2.0

²The amines of formula (I) and the mol ratio of glyphosate a.e..

Embodiment 11

Assessment embodiment 8 (comprises N-octyl group-N in greenhouse test, N-Dimethyl Ammonium glyphosate) and 9 (contain N-coconut alkyl-N, the herbicide action of composition N-Dimethyl Ammonium glyphosate), specifically be to representational annual broadleaf weed piemarker (Abutilon theophrasti with the above-mentioned composition foliage applying, ABUTH) and annual narrow leaf Echinochloa weeds barnyardgrass (Echinochloa crus-galli, ECHCF) on.In order to compare, comprised in test following commercialization standard preparation:

MON0139, the aqueous solution of the list of glyphosate (isopropyl ammonium) salt contains the described salt of 62 weight %, and does not contain other preparation compositions beyond dewatering, and can derive from Monsanto company; With

Roundup ^The Ultra weed killer herbicide, the aqueous solution concentrate formulation of the list of glyphosate (isopropyl ammonium) salt contains the described salt of 41 weight %, also contains surfactant, and this product is sold with the name of agriculture weed killer herbicide by the Monsanto company of the U.S..

MON0139 contains about 680 gram acid equivalent/liter (g a.e./1) glyphosates, Roundup ^The Ultra weed killer herbicide contains 356g a.e./l.

The following step is used for greenhouse test.

With the seed kind of the plant variety of appointment at 85mm ²In the mixed soil in jar, these soil have passed through steam sterilization and have used 3.6Kg/m ³The 14-14-14NPK slow release fertilizer apply fertilizer in advance.Jar is placed in the greenhouse of subsurface irrigation.Emerge about 1 week of back, thinning as required comprises and removes any unhealthy or unusual plant, produces evenly continuous test tank.

Test period continues plant to be placed in the greenhouse, maximum 14 hours illumination of plant acceptance every day in the greenhouse.If natural daylight is not enough to satisfy a day requirement, use the artificial light sources of the about 475 trace moles (microeinsteins) of brightness to make up the difference.Exposure temperature is accurately control, but about 27 ℃ of average daytime, about 18 ℃ of night.During whole test, plant is carried out subsurface irrigation to guarantee enough soil moisture levels.Remain on about 50% in duration of test relative moisture.

Jar is distributed to different processing by the experimental design of completely random, carry out three times and repeat.One group of jar stays and does not carry out handling as blank, after a while the effect of evaluation process in view of the above.Use Roundup ^The processing of Ultra provides two groups to repeat for three times to guarantee that present composition herbicide action relatively had a reliable basis.

It is with having assembled TeeJet that glyphosate composition is administered to the blade face ^TMThe crawler belt atomizers spray of 9501E nozzle, the sprayed volume that this nozzle can be supplied 93 liters/acre (l/ha) down through the pressure that is aligned in 166 kPas (kPa).When plant 2-3 carries out dispenser during week.After the processing, jar is put back in the greenhouse until preparing assessment again.Be to handle back 15 days (DAT) in this embodiment.

Use the Aquo-composition of dilution to handle, the concentrate composition that the said composition dilute with water prepares in advance prepares.All more all carries out under same glyphosate equivalent.Calculating establishes an equation under the dilution factor basis of the required glyphosate concentrate composition of preparation plant treatment compositions

A＝RS/VC

Wherein A is the volume (ml) for preparing the glyphosate composition of adding for the preparation plant treatment compositions, R is the amount of application of expection glyphosate, with gram acid equivalent/hectare is unit (ga.e./l), S is the cumulative volume (ml) of the plant treatment compositions of preparation, V is the rate of application (l/ha) of plant treatment compositions, be commonly referred to as " sprayed volume ", C is the concentration (ga.e./l) of glyphosate in the glyphosate composition.

Be the assessment herbicide action, all by experienced technical staff's check, this technical staff writes down the inhibition percentage to all plants in the test, by relatively estimating the effectiveness of each processing with the plant of being untreated.No effect is represented in 0% inhibition, and 100% inhibition represents that all plants are dead fully.85% or the higher inhibition weeding that is generally considered to be standard use acceptable; Yet in greenhouse test, in the described test of present embodiment, it is normal using composition with the expection generation less than 85% inhibiting consumption, because the composition that this easier difference has different effort levels.

The results are shown in the following table 3 of embodiment 11 tests.

The herbicide action data of table 3: embodiment 11

Glyphosate composition	Glyphosate consumption ga.e./l	Inhibitory action %
		Inhibitory action %		??ABUTH	????ECHCF
		???????MON0139	??????200	??ABUTH	????ECHCF	????0	????50
??????400	????2		??????200	????62		????0	????50
??????400	????2		??????600	????62	????43	????75
??????800	????72		??????600	????77	????43	????75
??????800	????72		??????1000	????77	????83	????85
?Roundup ^Ultra (first group)	??????200		??????1000	????20	????83	????85	????50
	??????200	??????400	????57	????20	????60		????50
	??????600	??????400	????57	????75	????60	????82
	??????600	??????800	????88	????75	????93	????82
	??????1000	??????800	????88	????95	????93	????94
	??????1000	?Roundup ^Ultra (second group)	??????200	????95	????5	????94	????67
	??????400	?Roundup ^Ultra (second group)	??????200	????33	????5	????73	????67
	??????400		??????600	????33	????72	????73	????83
	??????800		??????600	????87	????72	????85	????83
	??????800		??????1000	????87	????90	????85	????96
Embodiment 8 compositions	??????200		??????1000	????2	????90	????37	????96
	??????200	??????400	????27	????2	????50	????37
	??????600	??????400	????27	????60	????50	????53
	??????600	??????800	????88	????60	????70	????53
	??????1000	??????800	????88	????85	????70	????80
	??????1000	Embodiment 9 compositions	??????200	????85	????3	????80	????37
??????400	????67		??????200	????50	????3		????37
??????400	????67		??????600	????50	????77	????62
??????800	????83		??????600	????67	????77	????62
??????800	????83		??????1000	????67	????88	????73

In this test, under identical glyphosate a.e. consumption, N-octyl group-N, N-Dimethyl Ammonium glyphosate (embodiment 8) and N-coconut alkyl-N, the herbicide action that the colloidal dispersion of N-Dimethyl Ammonium glyphosate (embodiment 9) provides is better than glyphosate isopropyl ammonium (MON0139).Yet the herbicide action of these colloidal dispersions is not as the commercialization standard Roundup in this test ^The Ultra preparation.

Embodiment 12

Carry out according to used essentially identical step among the embodiment 11, except the following content that will note: in greenhouse test, foliage applying to two kind of typical annual broadleaf weed corn radish (Raphanus sativus, RAPSN) and Pharbitis purpurea (Ipomoea purpurea, PHBPU) and typical perennial grassy weed couchgrass (Elymus repens, AGRRE) on.Soil 3.9kg/m ³6-7-8NPK fertilizer apply fertilizer in advance.Plant is accepted 16 hours sunlight every day.Day temperature remains on about 23 ℃, about 18 ℃ of night.Relative moisture keeps about 70%.The Roundup that one group of three repetition is only arranged in this test ^Ultra.Herbicide action be evaluated at 5DAT in early days the time carry out, as the index that strengthens the early development sign.When 22DAT, carry out the assessment in late period.The composition that this test comprises is the composition of embodiment 8 (containing N-octyl group-N, N-Dimethyl Ammonium glyphosate) and 9 (containing N-coconut alkyl-N, N-Dimethyl Ammonium glyphosate).Embodiment 12 the results are shown in the following table 4.

The herbicide action data of table 4: embodiment 12

Glyphosate composition	Glyphosate consumption ga.e./ha	Inhibitory action %
		Inhibitory action %					???????5DAT		??????????22DAT
		?RAPSN	?PHBPU	?AGRRE	?RAPSN	?PHBPU	???????5DAT		??????????22DAT
		?RAPSN	?PHBPU	?AGRRE	?RAPSN	?PHBPU	MON?0139	????360	????10	??18	??43	????28	????30
????540	????10	??15	??55	????35	????32			????360	????10	??18	??43	????28	????30
????540	????10	??15	??55	????35	????32	????720		????10	??17	??47	????40	????32
RoundupUltra	????360	????17	??20	??67	????47	????720		????10	??17	??47	????40	????32	????73
	????360	????17	??20	??67	????47	????540	????30	??23	??67	????63	????80		????73
	????720	????23	??38	??75	????88	????540	????30	??23	??67	????63	????80	????95
	????720	????23	??38	??75	????88	Embodiment 8 compositions	????360	????20	??15	??55	????43	????95	????23
????540	????27	??17	??78	????53	????32		????360	????20	??15	??55	????43		????23
????540	????27	??17	??78	????53	????32		????720	????15	??15	??72	????67	????37
Embodiment 9 compositions	????360	????33	??35	??65	????73		????720	????15	??15	??72	????67	????37	????63
	????360	????33	??35	??65	????73	????540	Free of data	Free of data	Free of data	Free of data	Free of data		????63
	????720	????62	??55	??88	????87	????540	Free of data	Free of data	Free of data	Free of data	Free of data	????92

In this test, under identical glyphosate a.e. consumption, herbicide action and commercialization standard Roundup that N-octyl group-N, the colloidal dispersion of N-Dimethyl Ammonium glyphosate (embodiment 8) provide to AGRRE ^The Ultra preparation is similar.N-coconut alkyl-N, the colloidal dispersion of N-Dimethyl Ammonium glyphosate (embodiment 9) generally speaking is higher than the composition of embodiment 8 to the effectiveness of all three kinds of weeds.The early development sign of embodiment 9 compositions is significantly more than Roundup ^Ultra.

Embodiment 13

According to used essentially identical step among the embodiment 11, the blade face is administered on ABUTH and the ECHCF in greenhouse test.Herbicide action be evaluated at 21DAT the time carry out.The composition that this test comprises is the composition of embodiment 9 (containing N-coconut alkyl-N, N-Dimethyl Ammonium glyphosate) and 10 (containing N-tallow alkyl-N, N-Dimethyl Ammonium glyphosate).Embodiment 13 the results are shown in the following table 5.

The herbicide action data of table 5: embodiment 13

Glyphosate composition	Glyphosate consumption ga.e./ha	Inhibitory action %
		Inhibitory action %		??ABUTH	??ECHCF
		MON?0139	????200	??ABUTH	??ECHCF	????0	????50
????400	????20		????200	????77		????0	????50
????400	????20		????600	????77	????45	????87
????800	????47		????600	????88	????45	????87
????800	????47		????1000	????88	????73	????95
Roundup () Ultra (first group)	????200		????1000	????25	????73	????95	????77
	????200	????400	????50	????25	????95		????77
	????600	????400	????50	????63	????95	????98
	????600	????800	????92	????63	????100	????98
	????1000	????800	????92	????100	????100	????100
	????1000	Roundup () Ultra (second group)	????200	????100	????10	????100	????80
????400	????40		????200	????97	????10		????80
????400	????40		????600	????97	????60	????99
????800	????90		????600	????100	????60	????99
????800	????90		????1000	????100	????98	????100
Embodiment 9 compositions	????200		????1000	????5	????98	????100	????82
	????200	????400	????50	????5	????94		????82
	????600	????400	????50	????75	????94	????97
	????600	????800	????77	????75	????99	????97
	????1000	????800	????77	????87	????99	????100
	????1000	Embodiment 10 compositions	????200	????87	????33	????100	????82
????400	????75		????200	????83	????33		????82
????400	????75		????600	????83	????78	????87
????800	????83		????600	????90	????78	????87
????800	????83		????1000	????90	????83	????85

In this test, under identical glyphosate a.e. consumption, N-coconut alkyl-N, N-Dimethyl Ammonium glyphosate (embodiment 9) and N-tallow alkyl-N, the herbicide action to ABUTH that the colloidal dispersion of N-Dimethyl Ammonium glyphosate (embodiment 10) provides is comparable to Roundup ^Ultra.

Embodiment 14

Step according to embodiment 8 prepares comparative composition, and amines wherein is lauryl amine (Noram ^TM12D).The addition of lauryl amine is 9.4g, and glyphosate is 12.0g, and distilled water is 206g.Just before adding distilled water, add the 12g isopropyl alcohol.The pH of said composition is 4.5, and wherein the mol ratio of lauryl amine and glyphosate a.e. is 0.72: 1.Be muddy in appearance but do not show and be separated.The particle mean size of measuring aggregation is 2.0nm.

For comparing the present composition (composition of embodiment 10, contain N-tallow alkyl-N, N-Dimethyl Ammonium glyphosate) with the herbicide action of comparative composition, according to embodiment 12 in essentially identical step carry out greenhouse test, with the above-mentioned composition foliage applying on RAPSN, PHBPU and AGRRE.The Roundup that one group of three repetition is only arranged in this test ^Ultra.Herbicide action be evaluated at 22DAT the time carry out.Embodiment 14 the results are shown in the following table 6.

The herbicide action data of table 6: embodiment 14

Glyphosate composition	Glyphosate consumption ga.e./ha	Inhibitory action %
		Inhibitory action %			??AGRRE	??RAPSN	??PHBPU
		MON?0139	????360	????53	??AGRRE	??RAPSN	??PHBPU	????48	????43
????540	????57		????360	????53	????57	????47		????48	????43
????540	????57		????720	????65	????57	????47	????78	????57
RoundupUltra	????360		????720	????65	????78	????58	????78	????57	????58
	????360	????540	????88	????95	????78	????58	????58		????58
	????720	????540	????88	????95	????97	????83	????58	????65
	????720	Embodiment 10 compositions	????360	????97	????97	????83	????77	????65	????80
????540	????99		????360	????97	????75	????83	????77		????80
????540	????99		????720	????99	????75	????83	????82	????93
Comparative composition (lauryl ammonium salt)	????360		????720	????99	????55	????53	????82	????93	????53
	????360	????540	????70	????53	????55	????53	????52		????53
	????720	????540	????70	????53	????80	????55	????52	????57

N-tallow alkyl-N, the colloidal dispersion of N-Dimethyl Ammonium glyphosate (embodiment 10) herbicide action on AGRREh PHBPU at least is better than Roundup ^Ultra.On the contrary, the herbicide action of comparative composition that contains N-lauryl ammonium glyphosate is much weak, and is similar to effect and the MON0139 of RAPSN and PHBPU, and the effect of AGRRE only slightly is better than MON0139.

Embodiment 15

Be prepared as follows a series of compositions, the mol ratio of all alkali and glyphosate is 1: 1 in the described composition.At first, according to two kinds of compositions of general step preparation of embodiment 1, composition 15-5 uses N-decyl-N, and N-dimethyl amine and composition 15-10 use N-coconut alkyl-N, N-dimethyl amine (Noram ^TMDMC D).The preparation these two kinds of compositions in separately amines and the mol ratio of glyphosate a.e. be 1: 1.

Then, (form with MON 0139 adds with glyphosate isopropyl amine salt separately to prepare these compositions, wherein the mol ratio of isopropylamine and glyphosate a.e. is about 1: 1) mixture, thereby provide N-decyl-N, N-dimethyl amine or N-coconut alkyl-N, the mol ratio of N-dimethyl amine and glyphosate a.e. is lower than 1: 1 Aquo-composition.All compositions are 10 weight %a.e. preparations according to glyphosate content.The composition of preparation is:

15-1 N-decyl-N, N-dimethyl amine mol ratio 0.02: 1

15-2 N-decyl-N, N-dimethyl amine mol ratio 0.1: 1

15-3 N-decyl-N, N-dimethyl amine mol ratio 0.25: 1

15-4 N-decyl-N, N-dimethyl amine mol ratio 0.5: 1

15-5 N-decyl-N, N-dimethyl amine mol ratio 1: 1

15-6 N-coconut alkyl-N, N-dimethyl amine mol ratio 0.02: 1

15-7 N-coconut alkyl-N, N-dimethyl amine mol ratio 0.1: 1

15-8 N-coconut alkyl-N, N-dimethyl amine mol ratio 0.25: 1

15-9 N-coconut alkyl-N, N-dimethyl amine mol ratio 0.5: 1

15-10 N-coconut alkyl-N, N-dimethyl amine mol ratio 1: 1

The mol ratio of the composition 15-6 to 15-10 that attention provides above comprises the amines with the various alkyl chain lengths that derive from cocoa butter.If only consider C ₁₄Or the amines of long-chain more, estimate that corresponding mol ratio needs multiply by above-mentioned mol ratio with 0.3.For example, for composition 15-7, contain C ₁₄Or more the amines of long-chain and the mol ratio of glyphosate a.e. are about 0.03: 1.

At last, preparation is wherein used in the salt acid substitution glyphosate and N-coconut alkyl-N corresponding to " blank " composition of embodiment 9 compositions, and the N-dimethyl amine forms N-coconut alkyl-N, the aqueous solution of N-alkyl dimethyl ammonium chloride or dispersion.

According to used essentially identical step among the embodiment 11, the blade face is administered on ABUTH and the ECHCF in greenhouse test.Herbicide action be evaluated at 16DAT the time carry out.This test comprises the composition of embodiment 9, and said composition prepares by mixed aforesaid embodiment 9 " blank " and MON0139 before using facing, and obtains N-coconut alkyl-N, and the mol ratio of N-dimethyl amine and glyphosate a.e. is 1.19.This mol ratio can be found in the composition of embodiment 9.This test also comprises above listed composition 15-1 to 15-10.Embodiment 15 the results are shown in the following table 7.

The herbicide action data of table 7: embodiment 15

Glyphosate composition	Glyphosate consumption ga.e./ha	Inhibitory action %
		Inhibitory action %		??ABUTH	??ECHCF
		MON0139	????50	??ABUTH	??ECHCF	????0	????2
????100	????5		????50	????30		????0	????2
????100	????5		????200	????30	????72	????53
????400	????82		????200	????70	????72	????53
????400	????82		????600	????70	????87	????77
Roundup  Ultra (first group)	????50		????600	????0	????87	????77	????52
	????50	????100	????67	????0	????80		????52
	????200	????100	????67	????85	????80	????98
	????200	????400	????95	????85	????100	????98
	????600	????400	????95	????100	????100	????100
	????600	Roundup  Ultra (second group)	????50	????100	????0	????100	????55
????100	????60		????50	????78	????0		????55
????100	????60		????200	????78	????83	????99
????400	????97		????200	????100	????83	????99
????400	????97		????600	????100	????100	????100

Glyphosate composition	Glyphosate consumption ga.e./ha	Inhibitory action %
		Inhibitory action %		?ABUTH	??ECHCF
		Embodiment 9 composition coconut-N (Me) ₂, 1.19: 1 mol ratios	????50	?ABUTH	??ECHCF	????0	????60
????100	????58		????50	????83		????0	????60
????100	????58		????200	????83	????80	????98
????400	????90		????200	????100	????80	????98
????400	????90		????600	????100	????99	????100
The blank ＂ of the ＂ of embodiment 9+MON0139 coconut-N (Me) ₂, 1.19: 1 mol ratios	????50		????600	????0	????99	????100	????65
	????50	????100	????57	????0	????82		????65
	????200	????100	????57	????83	????82	????99
	????200	????400	????92	????83	????100	????99
	????600	????400	????92	????99	????100	????100
	????600	15-1 C10-N(Me) ₂, 0.02: 1 mol ratio	????50	????99	????0	????100	????5
????100	????18		????50	????33	????0		????5
????100	????18		????200	????33	????72	????58
????400	????85		????200	????77	????72	????58
????400	????85		????600	????77	????92	????83
15-2 C10-N(Me) ₂, 0.1: 1 mol ratio	????50		????600	????0	????92	????83	????0
	????50	????100	????25	????0	????38		????0
	????200	????100	????25	????73	????38	????58
	????200	????400	????90	????73	????83	????58
	????600	????400	????90	????95	????83	????83
	????600	15-3 C10-N(Me) ₂, 0.25: 1 mol ratio	????50	????95	????0	????83	????5
????100	????20		????50	????37	????0		????5
????100	????20		????200	????37	????73	????60
????400	????87		????200	????83	????73	????60
????400	????87		????600	????83	????92	????98
15-4 C10-N(Me) ₂, 0.5: 1 mol ratio	????50		????600	????0	????92	????98	????8
	????50	????100	????27	????0	????27		????8
	????200	????100	????27	????75	????27	????65
	????200	????400	????88	????75	????90	????65
	????600	????400	????88	????97	????90	????99
	????600	15-5 C10-N(Me) ₂, 1: 1 mol ratio	????50	????97	????0	????99	????13
????100	????30		????50	????23	????0		????13
????100	????30		????200	????23	????75	????55
????400	????87		????200	????88	????75	????55
????400	????87		????600	????88	????97	????100

Glyphosate composition	Glyphosate consumption ga.e./ha	Inhibitory action %
		Inhibitory action %		??ABUTH	??ECHCF
		15-6 coco-N(Me) ₂, 0.02: 1 mol ratio	????50	??ABUTH	??ECHCF	????0	????20
????100	????15		????50	????57		????0	????20
????100	????15		????200	????57	????70	????80
????400	????82		????200	????100	????70	????80
????400	????82		????600	????100	????98	????100
15-7 oco-N(Me) ₂, 0.1: 1 mol ratio	????50		????600	????0	????98	????100	????40
	????50	????100	????25	????0	????72		????40
	????200	????100	????25	????68	????72	????99
	????200	????400	????92	????68	????100	????99
	????600	????400	????92	????99	????100	????100
	????600	15-8 coco-N(Me) ₂, 0.25: 1 mol ratio	????50	????99	????0	????100	????62
????100	????27		????50	????77	????0		????62
????100	????27		????200	????77	????80	????99
????400	????92		????200	????100	????80	????99
????400	????92		????600	????100	????97	????100
15-9 coco-N(Me) ₂, 0.5: 1 mol ratio	????50		????600	????0	????97	????100	????50
	????50	????100	????40	????0	????73		????50
	????200	????100	????40	????82	????73	????99
	????200	????400	????90	????82	????100	????99
	????600	????400	????90	????96	????100	????100
	????600	15-10 coco-N(Me) ₂, 1: 1 mol ratio	????50	????96	????0	????100	????52
????100	????43		????50	????70	????0		????52
????100	????43		????200	????70	????80	????97
????400	????87		????200	????100	????80	????97
????400	????87		????600	????100	????99	????100

In this test, N-coconut alkyl-N, the herbicide action to ABUTH and ECHCF that the colloidal dispersion of N-Dimethyl Ammonium glyphosate (embodiment 9) provides equals commercial standard Roundup at least ^Ultra.By simple mixed N-coconut alkyl-N, the N-alkyl dimethyl ammonium chloride is own identical with composition 9 at least with the herbicide action of the composition that isopropyl ammonium glyphosate (" blank "+MON 0139 of embodiment 9) forms.

In a word, with N-decyl-N, the herbicide action that the composition (15-1 to 15-5) of N-Dimethyl Ammonium glyphosate preparation shows is lower than with N-coconut alkyl-N, the composition (15-6 to 15-10) of N-Dimethyl Ammonium glyphosate preparation.Yet, 0.02: 1 mol ratio when (15-6), N-coconut alkyl-N, N-Dimethyl Ammonium glyphosate is more effective unlike MON0139.In the mol ratio of 0.1: 1 and Geng Gao, N-coconut alkyl-N, the herbicide action that N-Dimethyl Ammonium glyphosate shows near or equal commercial standard Roundup ^Ultra.Surprisingly, the highest mol ratio does not demonstrate the strongest herbicide action, and generally speaking the optimal representation in this series is 0.25: 1 mol ratio (15-8).

Embodiment 16

According to the general step of embodiment 1, use N-octadecyl-N, N-dimethyl amine (ADMA-18 of Albemarle) is as preparing composition with glyphosate in the amines.Calculate N-octadecyl-N, the mol ratio of N-dimethyl amine and glyphosate is 1.37: 1.When the concentration that is diluted with water to glyphosate a.e. is 0.5 weight %, find that by dynamic light scattering composition contains globular micelle, its average diameter is 5nm, finds that by static light scattering the average weight of this globular micelle is 85000 dalton.Common micella contains the N-octadecyl-N of about 200 molecules as calculated, and the glyphosate of N-dimethyl amine and about 150 molecules, described N-octadecyl-N, N-dimethyl amine are protonated and the sum of protonated form not.

Embodiment 17

According to the general step of embodiment 1, use following amines to prepare a series of compositions with amine/glyphosate a.e. mol ratio of indicating:

N-coconut alkyl-N, N-dimethyl amine (coconut-NMe ₂) mol ratio 1.19: 1

N-tallow alkyl-N, N-dimethyl amine (butter-NMe ₂) mol ratio 1.56: 1

N-decyl-N, N-dimethyl amine (C ₁₀-NMe ₂) mol ratio 1.10: 1

N-dodecyl-N, N-dimethyl amine (C ₁₂-NMe ₂) mol ratio 1.23: 1

N-myristyl-N, N-dimethyl amine (C ₁₄-NMe ₂) mol ratio 1.08: 1

N-cetyl-N, N-dimethyl amine (C ₁₆-NMe ₂) mol ratio 1.28: 1

N-octadecyl-N, N-dimethyl amine (C ₁₈-NMe ₂) mol ratio 1.37: 1

N-oleyl-N, N-dimethyl amine (C ₁₈=NMe ₂) mol ratio 1.12: 1

According to used essentially identical step among the embodiment 11, the blade face is administered on ABUTH and the ECHCF in greenhouse test, except including only one group of Roundup ^Ultra handles.Herbicide action be evaluated at 15DAT the time carry out.Embodiment 17 the results are shown in the following table 8.

The herbicide action data of table 8: embodiment 17

Glyphosate composition	Glyphosate consumption ga.e./ha	Inhibitory action %
		Inhibitory action %		?ABUTH	?ECHCF
		MON0139	????50	?ABUTH	?ECHCF	????0	????0
????100	????0		????50	????5		????0	????0
????100	????0		????200	????5	????73	????25
????400	????90		????200	????55	????73	????25
????400	????90		????600	????55	????93	????68
RoundupUltra	????50		????600	????2	????93	????68	????3
	????50	????100	????70	????2	????62		????3
	????200	????100	????70	????90	????62	????91
	????200	????400	????99	????90	????100	????91
	????600	????400	????99	????100	????100	????99
	????600	coco-N(Me) ₂	????50	????100	????5	????99	????15
????100	????60		????50	????52	????5		????15
????100	????60		????200	????52	????87	????87
????400	????99		????200	????99	????87	????87
????400	????99		????600	????99	????100	????100
tallow.N(Me) ₂	????50		????600	????30	????100	????100	????53
	????50	????100	????80	????30	????80		????53
	????200	????100	????80	????93	????80	????98
	????200	????400	????99	????93	????98	????98
	????600	????400	????99	????98	????98	????99
	????600	C ₁₀-NMe ₂	????50	????98	????0	????99	????3
????100	????2		????50	????13	????0		????3
????100	????2		????200	????13	????77	????63
????400	????93		????200	????92	????77	????63
????400	????93		????600	????92	????98	????99
C ₁₂-NMe ₂	????50		????600	????0	????98	????99	????3
	????50	????100	????20	????0	????48		????3
	????200	????100	????20	????80	????48	????80
	????200	????400	????97	????80	????100	????80
	????600	????400	????97	????96	????100	????98

Glyphosate composition	Glyphosate consumption ga.e./ha	Inhibitory action %
		Inhibitory action %		??ABUTH	?ECHCF
		C ₁₄-NMe ₂	????50	??ABUTH	?ECHCF	????2	????10
????100	????45		????50	????67		????2	????10
????100	????45		????200	????67	????85	????90
????400	????99		????200	????98	????85	????90
????400	????99		????600	????98	????99	????96
C ₁₆-NMe ₂	????50		????600	????0	????99	????96	????48
	????50	????100	????43	????0	????65		????48
	????200	????100	????43	????88	????65	????85
	????200	????400	????99	????88	????98	????85
	????600	????400	????99	????99	????98	????93
	????600	C ₁₈-NMe ₂	????50	????99	????0	????93	????50
????100	????50		????50	????70	????0		????50
????100	????50		????200	????70	????87	????93
????400	????98		????200	????96	????87	????93
????400	????98		????600	????96	????99	????97
C ₁₈=NMe ₂	????50		????600	????0	????99	????97	????53
	????50	????100	????70	????0	????73		????53
	????200	????100	????70	????92	????73	????97
	????200	????400	????95	????92	????96	????97
	????600	????400	????95	????100	????96	????92

In this test, N-coconut alkyl-N, N-Dimethyl Ammonium glyphosate (coconut-NMe ₂) colloidal dispersion herbicide action and the commercial standard Roundup that provide to ABUTH and ECHCF ^Ultra is similar.N-tallow alkyl-N, N-Dimethyl Ammonium glyphosate (butter-NMe ₂) the herbicide action that provides of colloidal dispersion be better than commercial standard Roundup ^Ultra.

N-dodecyl-N, N-Dimethyl Ammonium glyphosate (C ₁₂-NMe ₂) herbicide action that provides is not as Roundup ^Ultra or N-coconut alkyl-N, N-Dimethyl Ammonium glyphosate (composition of coconut-NMe2), N-decyl-N, N-Dimethyl Ammonium glyphosate (C ₁₀-NMe ₂) effectiveness of composition is more weak.Believe at coconut-NMe ₂The middle C that exists ₁₄More long-chain is the reason that forms this composition high herbicidal activity level.Evidence is found in the N-myristyl-N of glyphosate in this test, N-Dimethyl Ammonium (C ₁₄-NMe ₂), N-cetyl-N, N-Dimethyl Ammonium (C ₁₆-NMe ₂), N-octadecyl-N, N-Dimethyl Ammonium (C ₁₈-NMe ₂), N-oleyl-N, N-Dimethyl Ammonium (C ₁₈=NMe ₂) and N-tallow alkyl-N, N-Dimethyl Ammonium (butter-NMe ₂) the shown strong herbicide action of salt composite.

Embodiment 18

General step according to embodiment 1 prepares a series of compositions, wherein uses N-octadecyl-N, and N-dimethyl amine (C18-NMe2) is as amines, and the mol ratio of amines and glyphosate a.e. is 1.37: 1.In process, in every kind of composition, add a kind of following assistant agent compound: soybean propyl diester (mainly being the oleic acid propyl ester); Methyl oleate; Olive oil; Tributyl phosphate; Heptane; Dimethyl sulfoxide (DMSO) (DMS0); Toluene; Glycerine; Corn syrup; Gelatin; The polyethylene glycol of mean molecule quantity 400 (PEG-400); The polyethylene glycol of mean molecule quantity 3400 (PEG-3400).In all cases, the interpolation weight of assistant agent compound equals the content of glyphosate a.e..Also use N-octadecyl-N, the N-dimethyl amine, but need not a kind of composition of described assistant agent compound.

According to embodiment 11 essentially identical steps, the blade face is administered on ABUTH and the ECHCF in greenhouse test, except including only one group of Roundup ^Ultra handles.Herbicide action be evaluated at 14DAT the time carry out.Embodiment 18 the results are shown in the following table 9.

The herbicide action data P66 of table 9: embodiment 18

Glyphosate composition	Glyphosate consumption ga.e./l	Inhibitory action %
		Inhibitory action %		??ABUTH	??ECHCF
		?MON0139	????50	??ABUTH	??ECHCF	????0	????0
????100	????3		????50	????30		????0	????0
????100	????3		????200	????30	????70	????45
????400	????80		????200	????63	????70	????45
????400	????80		????600	????63	????94	????68
Roundup ^Ultra	????50		????600	????25	????94	????68	????25
	????50	????100	????77	????25	????55		????25
	????200	????100	????77	????92	????55	????80
	????200	????400	????98	????92	????99	????80
	????600	????400	????98	????100	????99	????97
	????600	C ₁₈-NMe ₂	????50	????100	????0	????97	????40
????100	????25		????50	????68	????0		????40
????100	????25		????200	????68	????82	????90
????400	????97		????200	????96	????82	????90
????400	????97		????600	????96	????98	????100
C ₁₈-NMe ₂+ oleic acid propyl ester	????50		????600	????0	????98	????100	????50
	????50	????100	????20	????0	????72		????50
	????200	????100	????20	????83	????72	????95
	????200	????400	????99	????83	????93	????95
	????600	????400	????99	????99	????93	????97
	????600	C ₁₈-NMe ₂+ methyl oleate	????50	????99	????0	????97	????50
????100	????3		????50	????68	????0		????50
????100	????3		????200	????68	????80	????80
????400	????98		????200	????93	????80	????80
????400	????98		????600	????93	????99	????96

Table 9 (continuing)

C ₁₈-NMe ₂+ olive oil	????50	????0	????50
	????50	????0	????50	????100	????27	????73
	????200	????83	????90	????100	????27	????73
	????200	????83	????90	????400	????99	????95
	????600	????100	????94	????400	????99	????95
	????600	????100	????94	C ₁₈-NMe ₂+ tributyl phosphate	????50	????0	????17
????100	????0	????65			????50	????0	????17
????100	????0	????65	????200		????77	????83
????400	????96	????93	????200		????77	????83
????400	????96	????93	????600		????98	????99
C ₁₈-NMe ₂+ heptane	????50	????0	????600		????98	????99	????2
	????50	????0	????100	????5	????62		????2
	????200	????80	????100	????5	????62	????87
	????200	????80	????400	????97	????99	????87
	????600	????98	????400	????97	????99	????97
	????600	????98	C ₁₈-NMe ₂+DMSO	????50	????0	????97	????43
????100	????27	????70		????50	????0		????43
????100	????27	????70		????200	????83	????87
????400	????96	????96		????200	????83	????87
????400	????96	????96		????600	????99	????100
C ₁₈-NMe ₂+ toluene	????50	????0		????600	????99	????100	????10
	????50	????0	????100	????13	????63		????10
	????200	????80	????100	????13	????63	????96
	????200	????80	????400	????97	????93	????96
	????600	????99	????400	????97	????93	????99
	????600	????99	C ₁₈-NMe ₂+ glycerine	????50	????0	????99	????0
????100	????12	????55		????50	????0		????0
????100	????12	????55		????200	????78	????83
????400	????96	????97		????200	????78	????83
????400	????96	????97		????600	????99	????97

Table 9 (continuing)

?C ₁₈-NMe ₂+ corn syrup	????50	????0	????8
	????50	????0	????8	????100	????47	????53
	????200	????80	????82	????100	????47	????53
	????200	????80	????82	????400	????93	????90
	????600	????99	????99	????400	????93	????90
	????600	????99	????99	?C ₁₈-NMe ₂+ gelatin	????50	????0	????8
????100	????18	????60			????50	????0	????8
????100	????18	????60	????200		????80	????78
????400	????88	????90	????200		????80	????78
????400	????88	????90	????600		????96	????93
?C ₁₈-NMe ₂+PEG-400	????50	????0	????600		????96	????93	????45
	????50	????0	????100	????77	????75		????45
	????200	????94	????100	????77	????75	????85
	????200	????94	????400	????98	????99	????85
	????600	????99	????400	????98	????99	????99
	????600	????99	?C ₁₈-NMe ₂+PEG-3400	????50	????0	????99	????50
????100	????72	????72		????50	????0		????50
????100	????72	????72		????200	????83	????88
????400	????96	????96		????200	????83	????88
????400	????96	????96		????600	????99	????100

In this test, strengthened N-octadecyl-N by add polyethylene glycol in composition, the herbicide action of the colloidal dispersion of N-Dimethyl Ammonium glyphosate is particularly to the herbicide action of ABUTH.PEG-400 and PEG-3400 have this effect.

Embodiment 19

According to embodiment 11 essentially identical steps, the blade face is administered on ABUTH and the ECHCF in greenhouse test.In this test, the composition of embodiment 9 is used with the form of bucket mix formulation separately or with various surfactants, described surfactant is respectively with 0.25 volume % of spray composite and the concentration of 1 volume %.The surfactant of test is:

● MON0818 (Monsanto company): based on polyoxyethylene (15) beef tallow amine;

● Plurafac ^TMA-38 (BASF): polyoxyethylene (27) C16-18 alkyl ether;

● Fluorad ^TMFC-754 (3M): cationic fluoro organic surface active agent, think to have C ₈F ₁₇SO ₂NH (CH ₂) ₃N-(CH ₃) ₃The Cl-structure;

● Agrimul ^TMPG-2069 (Henkel): C _9-11Alkyl poly glucoside contains average 1.6 glucose units.

Use glyphosate isopropyl amine salt (MON0139) to replace the composition of embodiment 9 to compare processing with bucket mix formulation form with same surfactant.Herbicide action be evaluated at 14DAT the time carry out.Embodiment 19 the results are shown in the following table 10.

The herbicide action data of table 10: embodiment 19

Glyphosate composition	Glyphosate consumption ga.e./l	Inhibitory action %
		Inhibitory action %		?ABUTH	?ECHCF
		MON0139	????50	?ABUTH	?ECHCF	????0	????2
????100	????33		????50	????13		????0	????2
????100	????33		????300	????13	????80	????67
Roundup ^Ultra (first group)	????50		????300	????7	????80	????67	????47
	????50	????100	????57	????7	????77		????47
	????300	????100	????57	????88	????77	????99
	????300	Roundup ^Ultra (second group)	????50	????88	????22	????99	????60
????100	????60		????50	????80	????22		????60
????100	????60		????300	????80	????96	????99
MON0139+0.25％MON0818	????50		????300	????17	????96	????99	????65
	????50	????100	????50	????17	????88		????65
	????300	????100	????50	????93	????88	????99
	????300	MON0139+1％MON0818	????50	????93	????25	????99	????73
????100	????75		????50	????83	????25		????73
????100	????75		????300	????83	????93	????100
MON0139+0.25％Plurafac ^TM?A-38	????50		????300	????40	????93	????100	????80
	????50	????100	????80	????40	????87		????80
	????300	????100	????80	????99	????87	????99
	????300	MON0139+1％Plurafac ^TM?A-38	????50	????99	????78	????99	????77
????100	????87		????50	????87	????78		????77
????100	????87		????300	????87	????100	????99
MON0139+0.25％Fluorad ^TMFC-754	????50		????300	????60	????100	????99	????55
	????50	????100	????85	????60	????70		????55
	????300	????100	????85	????99	????70	????98
	????300	MON0139+1％Fluorad ^TM?FC-754	????50	????99	????50	????98	????55
????100	????82		????50	????70	????50		????55
????100	????82		????300	????70	????98	????99

Table 10 (continuing)

MON0139+0.25％Agrimul ^TM?PG-2069	????50	????30	????72
	????50	????30	????72	????100	????35	????91
	????300	????85	??100	????100	????35	????91
	????300	????85	??100	MON0139+1％Agrimul ^TM?PG-2069	????50	????18	????67
????100	????63	????83			????50	????18	????67
????100	????63	????83	????300		????95	????100
The composition of embodiment 9	????50	????12	????300		????95	????100	????63
	????50	????12	????100	????68	????83		????63
	????300	????96	????100	????68	????83	????100
	????300	????96	Embodiment 9 compositions+0.25%MON0818	????50	????30	????100	????70
????100	????83	????96		????50	????30		????70
????100	????83	????96		????300	????99	????100
Embodiment 9 compositions+1%MON0818	????50	????65		????300	????99	????100	????77
	????50	????65	????100	????87	????90		????77
	????300	????100	????100	????87	????90	????100
	????300	????100	Embodiment 9 compositions+0.25%Plurafac ^TM?A-38	????50	????50	????100	????80
????100	????82	????93		????50	????50		????80
????100	????82	????93		????300	????100	????100
Embodiment 9 compositions+1%Plurafac ^TM?A-38	????50	????73		????300	????100	????100	????78
	????50	????73	????100	????93	????91		????78
	????300	????100	????100	????93	????91	????100
	????300	????100	Embodiment 9 compositions+0.25%Fluorad ^TM?FC-754	????50	????55	????100	????60
????100	????82	????88		????50	????55		????60
????100	????82	????88		????300	????98	????100

Table 10 (continuing)

Embodiment 9 compositions+1%Fluorad ^TM?FC-754	????50	????60	????60
	????50	????60	????60	????100	????87	????75
	????300	????99	????100	????100	????87	????75
	????300	????99	????100	Embodiment 9 compositions+0.25%Agrimul ^TM?PG-2069	????50	????50	????82
????100	????73	????92			????50	????50	????82
????100	????73	????92	????300		????99	????100
Embodiment 9 compositions+1%Agrimul ^TM?PG-2069	????50	????50	????300		????99	????100	????80
	????50	????50	????100	????75	????97		????80
	????300	????99	????100	????75	????97	????100

Embodiment 20

With 16.2g N-coconut alkyl-N, N-dimethyl amine (Noram ^TMDMC D), the glyphosate of 11.3g purity 98.5%, 72.6g MON0139 (aqueous solution of 62% glyphosate isopropyl ammonium salt) stir the moisture concentrate composition of mixed preparation.N-coconut alkyl-N, it is 0.33: 1 that the N-dimethyl amine calculates the mol ratio of glyphosate.Obtain containing the clear liquid of 44.4 weight % glyphosate a.e..

Above-mentioned description to specific embodiments of the present invention is not to be intended to list fully every embodiment of the present invention.One skilled in the art will realize that and to make amendment to specific embodiments as herein described that this modification also is within the scope of the invention.

Claims

1. a plant treatment compositions is used to be administered to plant leaf surface to cause biological respinse, and said composition comprises acceptable liquid-carrier on a kind of agricultural, wherein dissolves or disperseed the amines of anion xenobiotics and one or more formulas (I)

R wherein ¹Be alkyl, contain 6 to about 22 carbon atoms, and the R of all existence ¹At least 30% of group contains 14 to about 22 carbon atoms, R ²And R ³Be C independently _1-5Alkyl; Described composition

(a) amount that contains xenobiotics should be enough to when with about 10 consumptions to about 1000 liters of per hectares (1/ha) said composition being administered to plant leaf surface, causes biological respinse; With

(b) mol ratio of the formula that contains in the composition (I) amines and xenobiotics is about 0.01: 1 to about 0.8: 1.

2. the composition of claim 1, liquid-carrier wherein is a water.

3. the composition of claim 2, the wherein described alkyl R in each described amines ¹Contain 14 to about 22 carbon atoms.

4. the composition of claim 2, wherein in the general formula of described amines, R ²And R ³It is methyl.

5. the composition of claim 2, xenobiotics wherein is a kind of nematocide, is selected from 3,4,4-three fluoro-3-butenoic acids and N-(3,4,4-three fluoro-1-oxygen-3-cyclobutenyls) glycine.

6. the composition of claim 2, xenobiotics wherein is a weed killer herbicide.

7. the composition of claim 6, weed killer herbicide wherein is the N-phosphonomethylglycine.

8. the composition of claim 2 also comprises a kind of oil or oily mixture of amount of auxiliary.

9. the composition of claim 8, wherein said oil all has the chemical constitution corresponding to formula (IX)

R ¹⁴-CO-Y-R ¹⁵????(IX)

R wherein ¹⁴Be to contain 5 the alkyl of having an appointment, R to about 21 carbon atoms ¹⁵Be to contain 1 alkyl, R to about 14 carbon atoms ¹⁴And R ¹⁵The total number of carbon atoms be about 11 to about 27, Y is O or NH.

10. the composition of claim 10, wherein said grease separation be from methyl oleate, ethyl oleate, isopropyl myristate, isopropyl palmitate and butyl stearate.

11. the composition of claim 10, the content of wherein said oil and the weight ratio of xenobiotics are about 1: 100 to about 10: 1.

12. each composition among the claim 2-11, comprise moisture application media, wherein be the colloidal state supramolecular aggregation that is scattered here and there, described supramolecular aggregation comprises one or more amphoteric salts, this amphoteric salt contains the anion of xenobiotics and derives from the protonated cation of described amines, and first molal quantity of xenobiotics to be neutralized by described amines wherein removed 0 or second molal quantity that one or more alkali the amines of described first molal quantity of neutralization neutralize and the 0 or the 3rd molal quantity of the sour form that do not neutralized by any alkali is present in composition.

13. each composition among the claim 2-11, comprise a kind of water-bearing media, wherein be not the supramolecular aggregation that colloidal state is disperseed substantially, described aggregation comprises one or more amphoteric salts, and this amphoteric salt contains the anion of xenobiotics and derives from the protonated cation of described amines.

14. each composition among the claim 1-13, the mol ratio of wherein most amines and xenobiotics are about 0.1: 1 to about 0.5: 1.

15. each composition among the claim 1-13, the wherein described alkyl R in each described amines ¹Contain 14,16 or 18 carbon atoms.

16. each composition among the claim 1-13, wherein said amines are selected from N-coconut alkyl-N, N-dimethyl amine, N-tallow alkyl-N, N-dimethyl amine and composition thereof.

17. each composition among the claim 1-13, also comprise a kind of assistant agent compound, the molecular structure of this compound comprises the polyoxyethylene chain that a treaty has 2-100 ethylene oxide unit, and the mol ratio of this compound and xenobiotics is about 1: 10 to about 10: 1.

18. a solid concentrate composition comprises the anion xenobiotics of representing with acid equivalent of about 5 weight %-75 weight %, forms among the claim 2-13 each plant treatment compositions when said composition is dissolved or dispersed in an amount of water.

19. a liquid concentrating composition comprises the anion xenobiotics of representing with acid equivalent of about 5 weight %-50 weight %, when said composition forms among the claim 2-13 each plant treatment compositions during with an amount of water dilution.

20. a moisture concentrate composition comprises the anion xenobiotics of representing with acid equivalent of about 5 weight %-50 weight %, when said composition forms among the claim 2-13 each plant treatment compositions during with an amount of water dilution.

21. one kind is used for plant or is being present in the plant or the bioactive method of the initiation in the pathogene on the plant, parasite or the consumer organism, comprises the step that each plant treatment compositions among the claim 1-17 of biologic effective dose is administered to plant leaf blade.

22. a method that is used to kill or control undesired plant comprises that the Herbicidal combinations with the claim 6 of herbicidally effective amount or 7 is administered to the step of plant leaf blade.