CN86108939A - Plant growth regulator dispersions - Google Patents
Plant growth regulator dispersions Download PDFInfo
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- CN86108939A CN86108939A CN198686108939A CN86108939A CN86108939A CN 86108939 A CN86108939 A CN 86108939A CN 198686108939 A CN198686108939 A CN 198686108939A CN 86108939 A CN86108939 A CN 86108939A CN 86108939 A CN86108939 A CN 86108939A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
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Abstract
Contain the stabilization formulations that is dispersed in the moisture phosphonic acids plant growth regulator in the oil, be specially adapted to the sprayer unit of ultra low volume.
Description
The present invention relates to the dispersion of plant growth regualting composition, particularly contain the water formulation and the oil formulation of 2-halo ethane phosphonic acid compound steady in a long-term in wide environmental temperature range.
2-halo ethane phosphonic acid compound is well known the ability of coordinate plant growth and introduction was arranged, and for example United States Patent (USP) 3,879, and 188; 4,144,046,4,240,819; 4,352,689; 4,374,661 and 4,401,454.When these phosphonic acids plant growth regulator are used to plant, produce various reaction,, quicken the uniformly ripening of fruit, promote effect resistant to lodging, break apical dominance as increasing output, or the like, in a word, can think the reaction of ethene or ethylene type.
The phosphonic acids plant growth regulator compound of being paid the utmost attention to and widely using by people is that generic name is called the 2-chloroethene phosphonic acids of " ethephon (profit) ".For easy to use and being reduced to a minimum greater than the degradation that began to take place in 5 o'clock approximately in pH value, ethrel is usually with the solution form storage than higher concentration.The pH value of dense ethrel is approximately 1.0.Concentrated solution was diluted to the concentration of pH about 3.5 earlier traditionally before being administered to plant.
Handling the most frequently used ethephon solution of plant is the aqueous solution, and used instrument is exactly common spraying apparatus.Yet using method nearby for example adopts the spraying apparatus of ultralow volume, preferentially adopts the non-aqueous solution of active chemistry oil-based formulation, and operating efficiency is rather improved.Another advantage of ethrel oil-based formulation is better than the water formulation to the permeability of plant tissue.
The water evaporates that the specific question that the present invention tries hard to solve is the ethrel water formulation is rapid, and when using the ultra low volume device, just this thing happens sometimes for the ethrel water formulation.Evaporation consequently only has dried active substance to be sprayed on the plant so rapidly in some cases.
For this reason, the oil-based formulation for preparing this class phosphonic acids plant growth regulator need be considered 2 points: improve the permeability of plant tissue and allow the possibility that these plant growth regulator are used in combination with the ultra low volume device.Yet, in fact need to use anhydrous phosphonic acids plant growth regulator owing to produce the phosphonic acids preparation, be unwelcome so directly prepare phosphonic acids with oily thinner.The extremely moisture absorption of the highly acid phosphinic acid compounds of this class, it is difficult therefore to prepare anhydrous product, the expense costliness, and also be difficult to preserve.
Agricultural chemicals oil-based water-soluble liquid formulation is known in this field.Finishing this class emulsion of preparation or dispersion is that required oil, water, active component and emulsifier are mixed into required preparation with suitable amount.This class emulsion component is typically 30～80% oil (weight) and 10～40% water.The emulsifier consumption is less, seldom surpasses the 15%(weight of final component), concentration often is 4～10%.
The oil emu for preparing chemically stable phosphonic acids growth regulator is rather difficult because the pH value of this compounds is lower.This low pH value is impelled the degraded of emulsifier.Destroy the stability of emulsion rapidly, cause the generation of phase separation.This situation has seriously limited this class emulsion and has used as spray agent, because the phase separation of spray agent makes the phosphonic acids plant growth regulator produce bad dispersion in the operating area.
The separation of preparation composition also can impel the generation of the solid that can block spraying apparatus.The acidic components of preparation, very safe when it is dispersed in the oily carrier, as phase separation takes place, also can corrode spraying apparatus rapidly.
The invention provides the dispersion that contains 2-halo ethane phosphonic acid plant growth regulator, it is very stable and be particularly suitable for using the ultra low volume device.
The aqueous solution of 2-halo ethane phosphonic acid plant growth regulator is mixed and made into above-mentioned dispersion with surfactant oily and specifically quantity.In some composition, also contain cosurfactant.
Main purpose of the present invention provides the oil-based composition that contains 2-halo ethane phosphonic acid plant growth regulating compound, and they are at thermodynamics and chemically be stable, and can use for ultra low volume equipment.
Another object of the present invention is the oil-based formulation of these mixtures of preparation, and they (promptly are low to moderate approximately-10 ℃ paramount extremely about 35 ℃) and keep the stability in 2 years at least under ambient temperature conditions.
A further object of the present invention is the oil base dispersion of preparation 2-halo ethane phosphonic acid plant growth regulator, and they are easy to wash hold-up tank and device therefor.
The invention provides a kind of stable plant growth regulator composition, it comprises brookfield viscosity less than 800 centipoises with contain the dispersion that is not more than about 300 millimicrons of micelles, comprising:
A) phosphonic acids plant growth regulator about 10～50%(weight),
B) water-immiscible liquid basically about 20～60%(weight), it is not the solvent of described reactive compound, and the pH of reactive compound value scope be stable and
C) water about 5～25%(weight) and
D) about 10～40%(weight) when the pH of described reactive compound value, be stable hydrophobic surfactant or surfactant mixture.
Phosphonic acids plant growth regulator one speech used herein not only comprises 2-halo ethane phosphonic acid compound, as ethylene agent, but also comprises that it is used as whole derivatives of plant growth regulator.
Be applicable to that phosphonic acids plant growth regulator of the present invention is in United States Patent (USP) 3,879,188; 4,374,661; 4,401,454; The existing list of references of introducing and listing this paper in 4,240,819 and 4,352,689.
Preferred phosphonic acids plant growth regulator is a 2-chloroethene phosphonic acids, and generic name is " ethrel ".The ethrel that is suitable for is 5～95% the concentrated liquid that contains, and preferred concentrate contains about 60～80%(weight) the phosphonic acids plant growth regulator.
" dispersion " used herein, " colloid " and terms such as " emulsions " are meant on macroscopic view it is homogeneous phase, but then are the multiphase mixture of two kinds or multiple fine dispersion phase (being solid, liquid or gas) on microcosmic.Dispersion of the present invention typically comprises liquid-liquid mixture, and wherein a kind of liquid is the aqueous solution of growth regulating compound, and another kind of liquid then is " oil ", i.e. water-immiscible liquid basically.So-called " water-immiscible liquid basically " speech is meant and comprises all liq, when it mixes in ratio described in the present invention with water, do not stir or the emulsifier-free existence condition under, after balance, promptly be separated into two disperse phase.
Liquid-in-liquid dispersions is made up of two kinds of liquid, and first kind of liquid forms continuous phase, is wherein distributing equably and is containing the micelle of the second kind of liquid drop that forms discontinuous phase." micelle " is meant a kind of molecule aggregate, and wherein each surfactant molecule all contains alone the functional group with water and oil phase effect.Be called hydrophilic with the functional group of water effect or hate oil, the functional group that combines with oil phase then is called oleophylic or hydrophobic.If water is continuous phase, and oil is the inferior looks that is trapped in the micelle center, then dispersion is oil-in-water (O/W) type emulsion.At Water-In-Oil (W/O) type emulsion, also be called in " inverted emulsion ", oil is continuous phase, water then is time looks.Micelle in this inverted emulsion is " a contrary micelle ", and the hydrophilic component of surfactant surrounds the water center, and hydrophobic components and oil on every side work.
Preparation of the present invention is to have low viscous micro emulsion, and at thermodynamics with chemically be stable.About 10～200 millimicrons little micelle of preferential selection particle size, the light scattering that can produce denier.Therefore, most of micro emulsion of the present invention all is transparent, does not add coloured reagent or additive.In some cases, the diameter of this preparation micelle reaches 300 millimicrons approximately, and this kind micelle can produce light scattering, and makes the preparation shape that is translucent.
Preparation of the present invention must have very low viscosity, can preparation be sprayed onto on the target plant the most handy ultra low volume equipment of enough common sprayer units.According to the situation of equipment therefor, also can use the preparation of wide region viscosity.Brookfield viscosity be it is generally acknowledged too thick greater than the preparation of 800 centipoises, be not suitable for any habitual sprayer unit, if preparation is used for the ultra low volume device, then viscosity preferably is no more than about 300 centipoises, and it is better to be not less than 100 centipoises.(measuring viscosity is to use Brookfield RVT type viscosimeter under 25 ℃ of conditions, No. 4 axles, per minute 20 changes).
Used phosphonic acids plant growth regulator compound concentrations in preparation of the present invention, preferred range is about 10～50%(weight), concrete concentration then depends primarily on the preparation that plan is used, and especially depends on the special plant growth response of handled plant and desired acquisition.
In micro emulsion preparation of the present invention, continuous phase is oil, i.e. water-immiscible liquid basically, and it is not the solvent of used reactive compound, and is stable when the pH of growth regulator value.Though can allow some slight mixing, but water oil must be fully immiscible, so that in particular dispersion in the used water-oil factor, make the microcosmic phase of two dispersions in the preparation, add under the situation of the composition existence in the preparation at all, be about in-20 ℃～+ 50 ℃ scopes time that can keep one section continuity in temperature.Comparatively it is desirable to, dispersion can keep the mixing in 2 years at least in-10 ℃～+ 35 ℃ temperature range.In general, the meltage of oil in water should not surpass 1%(weight).In addition, the oil of selecting for use must be stable in be low to moderate 0.5 the acid medium that phosphinic acid compounds produced by pH.Do not wish in the present invention the compound to acidolysis or protonation sensitivity is used as oil.These compounds comprise ester, amine and pyridine compounds.With the oil of this class acid labile, especially under hot conditions, the long-time stability that reach more than 2 years or 2 years are to be difficult to realize.
Used oils is also tackled target plant under the concentration conditions of using be plant-less toxicity basically.Oils should be nontoxic, even toxic, it kills and wounds the required time of plant above the available or remaining season of growth of plant.In addition, if preparation is prepared to spray with ultra low volume equipment, then used oils is preferably fully unvaporized, thereby the droplet of preparation is sprayed on the target plant with liquid form.Therefore, must consider to be used for the vapour pressure of the oils of ultra low volume device.
In preparation of the present invention available representative oils be aromatic hydrocarbons, natural resources extract, contain nearly 30 carbon atoms, nearly 4 non-adjacent two keys and the aliphatic hydrocarbon of 4 halogens, carboxyl or hydroxyl substituents (certain, as to suppose that compound is a kind of water-immiscible liquid) nearly.The mixture of these oils also can adopt.Good especially oils comprises the mixture of alkane or isoparaffin; Contain nearly 4 C
1-C
4The benzene of alkyl substituent or alkylbenzene; The fatty acid that contains about 12～30 carbon atoms, for example oleic acid and linoleic acid and triglyceride derivative thereof; The extract of natural resources, i.e. tall oil, palm oil, cottonseed oil, Linseed oil, soybean oil, peanut oil, castor bean seed oil and lanolin.Above-listed oils only is as illustrations.Any oils with desired physical characteristic all can be used.
Special preparation be decided by some experience character of composition in the said preparation with oil mass.The consumption of the consumption Ying Yushui of oil is corresponding, makes oil form continuous phase in final preparation.The consumption of usually oil is calculated by weight the consumption that should surpass water, and in general, used weight percentage is approximately 20～60% oil.
Though in some cases, available relatively large water generally should not surpass 20%(weight).For example, in the composition of the oil that contains a small amount of (about 10%) growth regulator and a large amount of (about 30%) surfactants and significant quantity (about 35%), require with being about 25%(weight) water.But usually, the consumption of water seldom surpasses the 15%(weight of final preparation).
With regard to oil, under the low pH condition that is produced by phosphonic acids plant growth regulator compound, particularly under the very low pH condition that the preferential phosphonic acids plant growth regulator fortified aqueous that adopts is produced, hydrophobic surfactant must have chemical stability.In addition, surfactant must not can be brought up to the level that changes the reactive compound decomposition of leading to the pH value.In general, any hydrophobic cations, anion or the non-ionic surface active agent that can not improve the pH of system all may be utilized.Use the preparation of anion or non-ionic surface active agent as if can provide long-time stability preferably.
Because some contains esters surface active agent hydrolysis slowly can take place, if long term storage under hot conditions, can cause preparation rotten gradually, so must the careful surfactant of selecting for use.In addition, many cationic surfactants all have nitrogenous functional group, and these functional groups can cause the decomposition of preferred phosphinic acid compounds within a certain period of time.
The effect degree of water, oil and surfactant can be predicted by surfactant hydrophilic lipophilic balance (HLB).According to reports, the HLB value of most of surfactants is in 0～20 scope, and wherein 0～6 represents strong-hydrophobicity (or lipophile), the medium hydrophobicity of 6～10 expressions, 10～14 expression medium hydrophilies (or oil repellency), 14～20 expression strongly hydrophilics.
So surfactant is had hydrophobic requirement in composition of the present invention because oil properties is the most useful the generation.Replacement and unsubstituted aliphatic hydrocarbon and aromatic hydrocarbon and natural extract all are nonpolar or have only the material of some micropolars.In general, the liquid for preparing this class Water-In-Oil dispersion requires to have the hydrophilic surfactant active of high HLB, and promptly HLB is approximately 14～17.But, find that when having 10～50%2-halo ethane phosphonic acid to exist, this class surfactant can not produce stable microemulsion shape liquid.If the use hydrophobic surfactant, promptly HLB can overcome difficulties less than about 8 surfactant.
Being subjected under the constraint of any theory of advising being not intended to, can thinking that phosphonic acids forms the tendency of hydrogen bond with surfactant in water, is the reason that causes this surprising observation result.When acid during with water and Action of Surfactant, it is 13 or greater than 13 that the aggregation of surfactant that is generated and acid obviously has effective HLB value.When have the high surfactant of HLB value when using separately or with the surfactant bond in during as main component, effective HLB value can be brought up at all and can not be formed micro emulsion, even formed a kind of micro emulsion but its thermodynamic stability is short-lived.No matter what surfactant is with the mechanism of acid effect, is clear that now, and when the oil of selecting for use has the character of above-mentioned oils, the preparation and the stability of 2-halogen ethane phosphonic acid emulsion all need to use hydrophobic surfactant.
The representative surfactants that can be used in composition of the present invention is the glycerol derivatives that contains single base replacement of about 10～30 carbon atom fatty acids, as monostearate, and a monooleate and a lauric acid; The glycosyl derivative of fatty acid that in fatty acid chain, contains about 10～30 carbon atoms; The acetyl glycerine ester of natural oils (promptly by the liquid that extracts in the natural resources); The polyethoxy alcohol or the alkylphenol that contain about 6～30 carbon atom branched-chain or straight-chain alkyls.Ester, the phosphoric acid analog of phosphate and many these class reactants also can adopt.Stable hydrophobic amine or amide derivatives also can use effectively.
Particularly preferred surfactant is anion or the nonionic polyethoxylated derivative that contains the pure and mild phenol of the oxirane that is less than 20 moles in about 8～30 carbon atoms and every mol of alcohol or the phenol.
For dispersity and stability are reached to greatest extent, composition of the present invention requires to use the exhibiting high surface activating agent.And optimum amount must be determined by experience with use oil properties and consumption according to the consumption of growth regulator, and typical percetage by weight is about 10～40%.
It is exactly the tolerance that they change preparation HLB that a very beyond thought character is arranged in some micro emulsion of the present invention.Form the accurate ratio that stable dispersion requires oil, water and surfactant usually.Concerning micro emulsion, this particular importance.For example, if high polar liquid or very hydrophilic surfactant (promptly having the HLB value is more than 17 or 17) are added in the stable microemulsion shape liquid of non-polar oil, water and surfactant, because thermodynamical equilibrium is damaged, so dispersion will promptly be separated into phase immediately after being provided with.But the micro emulsion that contains 2-halo ethane phosphonic acid and hydrophobic surfactant allow to add the very hydrophilic anion of remarkable quantity or non-ionic surface active agent and does not lose its thermodynamic stability.If add nearly 9%(weight) very hydrophilic surfactant, contain few so to 10～15%(weight) the emulsion of hydrophobic surfactant will remain stable.This character has real advantage, because water just can be clean the equipment for washing that is used for spraying emulsion very simply.
Do not having under the situation of hydrophilic surfactant, the emulsion raffinate will be refused water, because hydrophobic surfactant is unusual hydrophobic, so when water is added spray appliance, the polymerization of emulsion residue is so water-immiscible liquid will stick on the wall of this equipment.Hydrophilic surfactant is added emulsion, the emulsion raffinate is mixed and the available water washes clean with water.
In order to prepare composition of the present invention, can add component by any step, but usually under ambient temperature conditions, must fully stir it is mixed until the formation micro emulsion.Sometimes may need to be heated to about 50 ℃.But if do not know the suitable quantity of growth regulator, oil, water or surfactant, if perhaps some special composition reacts thereby do not form micro emulsion after mixing, can add a kind of cosurfactant this moment.
" cosurfactant " is the non-ionizing organic compound of a kind of low-molecular-weight, and it contains polar functional group and can increase the interaction of surfactant, water and oil.Any time of cosurfactant in preparation process all can add mixture.But if in a special preparation, the ratio of oil and water is balance very accurately, so just can be with cosurfactant after growth regulator, water, surfactant and oil are mixed into coarse emulsion.When the cosurfactant titration is added emulsion, coarse emulsion should be carried out vigorous stirring and mix.Till titration lasts till that opaque coarse emulsion becomes transparent or translucent the time.If coarse emulsion is coloured, should check that so coarse emulsion changes some phenomenon of micro emulsion into, change in color or muddy the disappearance for example may be taken place.
Habitual cosurfactant is to contain 1 straight-chain fatty alcohol to about 6 carbon atoms.Be applicable to that of the present invention is side chain or straight chain C
1-C
15MHA or polyhydroxy-alcohol; Contain n-butanol, C
8-C
10The preparation of straight chain alcohol, ethylene glycol or propane diols can obtain special stable microemulsion shape liquid.Contain 4 C of as many as
1-C
3The urea of alkyl substituent and the urea of replacement and contain C
1-C
3The dioxane formamide of alkyl all can use; Urea and dimethyl formamide have proved effective especially.Contain C
1-C
6The trialkylphosphate of straight or branched alkyl also can use: tributyl phosphate then is a kind of effective cosurfactant.
When share with other components, the amount that is used for the cosurfactant of special preparation needs rule of thumb to determine.But the typical concentrations scope is about 5～30%.When using cosurfactant, the common reduction of the amount of required surfactant is about as much as without 5～10% of cosurfactant in the preparation.
Micro emulsion is generally not destroyed because of the use cosurfactant to the tolerance that the HLB of system changes.But we find: if preparation contains cosurfactant, then the surfactant that HLB is slightly high (being approximately 8～9) also can use.
Following embodiment further specifies purpose of the present invention.
A. the preparation that does not contain cosurfactant
Embodiment 1
With 3.6 grams, 70% moisture 2-chloroethene phosphonic acids, 3.6 gram aromatic hydrocarbons (aromatic 150, straight chain alcohol surfactant (the Alfonic 1412-40 of mixture Exxon) and 2 gram nonionic ethoxylations, Conoco) carry out chemical combination and concocting to transparency liquid and generate, be prepared into micro emulsion.In the time of 50 ℃, this micro emulsion all is stable on chemistry and thermodynamics.
Embodiment 2
Mixture, 3.5 gram nonionic ethoxylated linear alcohols surfactant (Alfonic 1412-40 with 3 gram isoparaffins (Isopar M.Exxon), Conoco) and 3.5 grams, 70% moisture 2-chloroethene phosphonic acids carry out chemical combination and concoct to transparency liquid generating, be prepared into micro emulsion.In the time of 50 ℃, this micro emulsion is stable on chemistry and thermodynamics.
Embodiment 3
(HAN, Exxon) (Alfonic 1412-40 Conoco) carries out chemical combination and transfers to transparency liquid generating with 2 grams, 70% moisture 2-chloroethene phosphonic acids the straight chain alcohol surfactant of compound, 3 gram nonionic ethoxylations, is prepared into micro emulsion with 3 gram aromatic hydrocarbons.In the time of 50 ℃, this micro emulsion is stable on chemistry and thermodynamics.
Embodiment 4
Straight chain alcohol surfactant (Alfonic 1412-40 with 5.3 gram isoparaffin (Isopar M.Exxon) mixtures, 2.8 gram nonionic ethoxylations, Conoco) and 1.9 grams, 70% moisture 2-chloroethene phosphonic acids carry out chemical combination and concoct to transparency liquid forming, be prepared into micro emulsion.In the time of 50 ℃, this micro emulsion is stable on chemistry and thermodynamics.
B. the preparation that contains cosurfactant
Embodiment 5
Add 30 gram tall oils (the L5 level, Westvaco), 10 gram complexing organophosphorus ester anion surfactants (Gafac surfactants (Gafac) RM-510, free acid GAF) and 10 gram straight chain C
9-C
11Alcohol mixture (Neodol 91, a species of small clam living in fresh water shell) is mixed to dissolution and finishes, and stirs to add 30 gram 70% moisture 2-chloroethene phosphonic acids and this coarse emulsion is added to isometric water, makes micro emulsion.This micro emulsion stability is very poor, is separated into two phases after several hours.
Embodiment 6
With 0.7 gram urea, the 4 gram 70%2-chloroethene phosphonic acids aqueous solution, 1 gram organophosphorus ester anion surfactant (Emphos CS-341, Witco) and 4 gram tall oils (the L5 level Westvaco), is shaken to clear liquid and is formed, and makes micro emulsion.This micro emulsion all is stable on chemistry and thermodynamics in-20 ℃～50 ℃ scopes.
Embodiment 7
With 4 gram tall oil (L5 levels, Westvaco), 1 gram organophosphorus ester anion surfactant (Emphos CS-341, Witco), nonyl phenol non-ionic surface active agent (the Tergitol NP-6 of 0.5 gram ethoxylation, the associating carbonization), 1.2 gram propane diols and 4 grams, 70% moisture 2-chloroethene phosphonic acids carry out chemical combination, be stirred to clear liquid and generate, make micro emulsion.This micro emulsion all is stable on chemistry and thermodynamics in the time of 50 ℃.
Embodiment 8
With the free acid of 5 gram oleic acid, 2 gram complexing organic phosphoric acid anion surfactants (Gafac surfactants PE-510, GAF), 1 gram urea and 5 grams, 70% moisture 2-chloroethene phosphonic acids carry out chemical combination, is mixed to clear liquid and generates, and makes micro emulsion.In the time of 50 ℃, this micro emulsion all is stable on chemistry and thermodynamics.
Embodiment 9
With 4 gram tall oil (L5 superfine, Westvaco), 1 gram organophosphorus ester anion surfactant (Emphos CS-341, Witco), 1 gram tributyl phosphate and 6 grams, 70% moisture 2-chloroethene phosphonic acids carry out chemical combination, is mixed to transparency liquid and generates, and makes micro emulsion.This micro emulsion all is stable on chemistry and thermodynamics in the time of 50 ℃.
Embodiment 10
With 4 gram tall oil (L5 A superfine, Westvaco), 1 gram organophosphorus ester anion surfactant (Emphos CS-341, Witco), 1 gram n-butanol and 6 grams, 70% moisture 2-chloroethene phosphonic acids carry out chemical combination, is mixed to transparency liquid and generates, and makes micro emulsion.In the time of 50 ℃, this micro emulsion all is stable on chemistry and thermodynamics.
C. contain the preparation that is added with the hydrophilic surfactant active
Embodiment 11
With 4.5 gram aromatic hydrocarbons (aromatic 150, Exxon) free acid (Gafac surfactants (Gafac) RM-410 of mixture, 1.1 gram complexing organophosphorus ester anion (hydrophobic) surfactants, GAF), 0.8 gram polyethoxy nonyl phenol (hydrophilic) surfactant (Arnox (Arnox) 950, Arjay) and 2.5 the gram 70% moisture 2-chloroethene phosphonic acids carry out chemical combination, be mixed to transparency liquid and generate, make micro emulsion.In the time of 50 ℃, this micro emulsion all is stable on chemistry and thermodynamics.The residue of staying in storage or the device therefor is easy to wash with water totally.
Embodiment 12
With poly-(ethyleneoxy) ethanol nonionic (hydrophobic) surfactant (the Emulphogene BC-420 of 2.5 gram tridecane oxygen bases, GAF), poly-(ethyleneoxy) ethanol nonionic (hydrophilic) surfactant (surfactant (Igepal) CO-997 of 1.8 gram Nonylphenoxies, GAF), 0.5 gram ethylene glycol, 3.4 gram isoparaffin (Isopar M, Exxon) mixture and 1.8 grams 70% contain 2-chloroethene phosphonic acids and carry out chemical combination, be mixed to transparency liquid and generate, make micro emulsion.In the time of 50 ℃, this micro emulsion is all to be stable on chemistry and thermodynamics.The residue of staying in storage or the equipment therefor is easy to wash with water totally.
Embodiment 13
With 2.5 gram nonionic ethoxylated linear alcohols surfactant (Alfonic 1412-40, Conoco), 1 gram methyl isoamyl ketone, the 3 gram 70%2-chloroethene phosphonic acids aqueous solution and 3 gram isoparaffin (Isopar M, Exxon) mixture carries out chemical combination, be mixed to transparency liquid and generate, make micro emulsion.In the time of 50 ℃, this micro emulsion all is stable on chemistry and thermodynamics.The residue of staying in storage and the device therefor is easy to wash with water totally.
Embodiment 14
With poly-(ethyleneoxy) ethanol nonionic (hydrophobic) surfactant (the Emulphogene BC-420 of 2.5 gram tridecane oxygen bases, GAF), poly-(ethyleneoxy) ethanol nonionic (hydrophilic) surfactant (the Igepal CO-997 of 1.5 gram Nonylphenoxies, GAF), 0.5 gram methyl isoamyl ketone, 2.5 gram isoparaffin (Isopar M, Exxon) mixture and the 3 gram 70%2-chloroethene phosphonic acids aqueous solution carry out chemical combination, be mixed to transparency liquid and generate, make micro emulsion.In the time of 50 ℃, this micro emulsion all is stable on chemistry and thermodynamics.Be easy to the residual washing-out in storage and the device therefor clean with water rinse.
Composition of the present invention can or be used after the oil dilution of natural resources extraction with pure form and be used for the ultra low volume device; Usually all dilute with cottonseed oil or soybean oil.The concentration of active component in the micro emulsion is depended in the decision of whether diluting, and uses the smooth degree of pure preparation and makes plant produce the concentration of the needed active component of desirable effect.Although the usual amounts of emulsion is 0.5～2 pound of effective ingredient/acre (a.i./A), once used approximately from 0.1 to cover degree up to 30 pounds (a.i./A).
Following embodiment is that explanation utilizes these compositions to regulate the growth of cotton plant.In these embodiments, T
0Expression medication day, T
1Represent the observation after 7 days, T
2Represent the observation after 14 days.
Embodiment A
Under sunny 82 calm temperature condition,, the preparation of embodiment 2 is sprayed in the piece of field 20 seedings has planted on precocious Stoneville 825 cotton plants of four first quarter moons by aircraft ultra low volume device.The cover degree of 2-chloroethene phosphonic acids is 1 pound (a.i./A).After two weeks, check the percentage (%) of percentage (%), green peach density and fallen leaves that treatment region mid portion cotton boll splits.Compare observation to undressed 6 row cotton plants with the field piece that conventional sprayer sprayed 1 pound of (a.i./A) 2-chloroethene phosphonic acids aqueous solution.The results are shown in the table I.
Embodiment B
Under sunny 82 calm temperature condition, by aircraft the preparation of embodiment 4 is sprayed in the piece of field 20 seedings with the ultra low volume device and has planted on precocious Stoneville 825 cotton plants of four first quarter moons.The cover degree of 2-chloroethene phosphonic acids is 0.5 pound (a.i./A).The treatment region mid portions are checked in two week backs, and cotton boll splits, the percentage (%) of green peach density and fallen leaves.Compare observation to undressed 6 row cottons with the field piece that conventional sprayer sprayed 1 pound of (a.i./A) 2-chloroethene phosphonic acids aqueous solution.The results are shown in the table I.
The table I
Split (%) green peach number/10 feet of cotton boll. row fallen leaves (%)
Embodiment T
0T
1T
2T
0T
1T
2T
0T
1T
2
A 72 98 100 39 3 0 40 99 98
Aq.ref.
＊A 52 70 99 75 33 5 31 83 90
B 60 97 100 45 3 1 55 96 96
Aq.ref.
＊B 69 73 96 48 22 5 31 83 89
UTC＊＊ 65-75 - - - - - 35＊＊＊
* Aq.ref=uses the reference aqueous solution of corresponding embodiment same coverage
*The undressed contrast of UTC=
* * observes some regeneration situation
When after under the condition of similarity same coverage 2-chloroethene phosphonic acids aqueous solution being imposed on the cotton field, to the cotton boll cracking, form and the influence of fallen leaves compares, by above-mentioned report, the difference of embodiment 2 and 4 micro emulsion may be very little.Obviously, composition of the present invention has identical effect with known growth regulator water formulation at least.Their attendant advantages is that available modern ultra low volume equipment is implemented.
Embodiment A and B the results are shown in the table I.The noticeable micro emulsion of embodiment A and B that is to use is compared with using the aqueous solution with amount, has improved effect.According to the observation in two weeks behind the spray medicine, the performance of microemulsion composition of the present invention is better than the aqueous solution.Moreover, if 7 days effect of preparation of the present invention then can be compared with the effect that application of water solution produced after 14 days at least not as good as the effect of the aqueous solution.
Claims (14)
1, a kind of composition of stable coordinate plant growth comprises having less than 800 centipoise brookfield viscosity and contain the dispersion that is not more than about 300 millimicrons of micelles, comprising:
A) the phosphonic acids plant growth regulator of about 10～50% (weight),
B) liquid of about 20～60% (weight), described liquid is:
I. basically with the water unmixing,
Ii. not the solvent of described conditioning agent,
Iii. be stable in the pH of described conditioning agent value, and
C) water of about 5～25% (weight),
D) hydrophobic surfactant of about 10～40% (weight) or surfactant mixture, it is stable in the pH of described conditioning agent value.
2, according to the composition of claim 1, wherein said phosphonic acids plant growth regulator is a 2-chloroethene phosphonic acids.
3, according to the composition of claim 1, wherein said brookfield viscosity is less than 300 centipoises.
4, according to the composition of claim 1, wherein said liquid is:
A. aromatic hydrocarbon,
B. the organic extract that from natural resources, obtains,
C. the aliphatic hydrocarbon that contains 30 carbon atoms of as many as, 4 non-adjacent two keys of as many as and as many as 4 halogens, carboxyl or hydroxyl substituents.
5, according to the composition of claim 4, wherein said liquid is alkane, isoparaffin, and benzene contains 4 C of as many as
1-C
4Substituent alkylbenzene contains the fatty acid or the triglyceride derivative of about 12～30 carbon atoms, tall oil, palm oil, cottonseed oil, Linseed oil, soybean oil, peanut oil, castor oil and lanolin or its mixture.
6, according to the composition of claim 1, wherein said surfactant is the mono-substituted glycerol derivatives that contains about 10～30 carbon atom fatty acids, the glycosyl derivative of fatty acid that in fatty acid chain, contains about 10～30 carbon atoms, the acetyl glycerine ester of natural oils, the polyethoxy alcohol or the alkylphenol that contain the branched-chain or straight-chain alkyl of about 6～30 carbon atoms, or its ester, phosphate, phosphoric acid, amine or amine, and any mixture.
7, according to the composition of claim 6, wherein said surfactant is to contain one or more anion or nonionic polyethoxy alcohol or the phenolic compounds that the oxirane that is less than 20 moles is arranged in about 8～20 carbon atoms and every mol of alcohol or the phenol in the alkane chain.
8, according to claim 1 composition and about 5～30%(weight) composition of cosurfactant.
9, composition according to Claim 8, wherein said cosurfactant are side chain or straight chain C
1-C
15Hydroxyl alcohol or polyhydroxy-alcohol, contain 4 C of as many as
1-C
3The urea of alkyl substituent or the urea of replacement contain C
1-C
3The dialkylformamide of alkyl or contain C
1-C
6The trialkylphosphate of straight or branched alkyl.
10, according to the composition of claim 9, wherein said cosurfactant is a n-butanol, C
8-C
10The mixture of alcohol, dimethyl formamide, 1,2 ethylene glycol, propane diols, or tributyl phosphate.
11,, also comprise as many as 10%(weight according to the composition of claim 1) hydrophilic surfactant active of hydrophilic lipophilic balance value (HLB) at least 16.
12, a kind of composition comprises about 20～30%(weight) 2-chloroethene phosphonic acids, about 7～14%(weight) water, about 35～40%(weight) aromatic hydrocarbon mixture and about 20～25%(weight) the nonionic ethoxylated linear alcohols.
13, a kind of composition comprises about 10～25%(weight) 2-chloroethene phosphonic acids, about 5～10%(weight) water, about 30～35%(weight) isoparaffins mixture and about 25～35%(weight) the nonionic ethoxylated linear alcohols.
14, a kind of composition, comprise about 15～25%(weight) 2-chloroethene phosphonic acids, about 7～10%(weight) water, about 50～55%(weight) aromatic hydrocarbon mixture, about 10～14%(weight) hydrophobic anion free acid and about 8～10%(weight of complexing organophosphorus ester) the hydrophily polyethoxylated nonylphenol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81489885A | 1985-12-30 | 1985-12-30 | |
| US814,898 | 1985-12-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86108939A true CN86108939A (en) | 1987-07-22 |
Family
ID=25216288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686108939A Pending CN86108939A (en) | 1985-12-30 | 1986-12-29 | Plant growth regulator dispersions |
Country Status (9)
| Country | Link |
|---|---|
| CN (1) | CN86108939A (en) |
| AU (2) | AU6890287A (en) |
| BR (1) | BR8607066A (en) |
| CA (1) | CA1282977C (en) |
| EG (1) | EG17951A (en) |
| GB (1) | GB2194226B (en) |
| TR (1) | TR22763A (en) |
| WO (1) | WO1987004047A1 (en) |
| ZA (1) | ZA869743B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103596433A (en) * | 2012-02-27 | 2014-02-19 | 生态研究所公司 | Use of a herbicidal composition for controlling parasitic plants |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19834598A1 (en) * | 1998-07-31 | 2000-02-03 | Hoechst Schering Agrevo Gmbh | Aqueous suspension concentrate containing thidiazuron and ethephon |
| AU1039000A (en) * | 1998-09-29 | 2000-04-17 | Aventis Cropscience S.A. | Method of sugarcane flower inhibition and new composition |
| DE10258867A1 (en) * | 2002-12-17 | 2004-07-08 | Bayer Cropscience Gmbh | Microemulsion concentrates |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PH9673A (en) * | 1970-11-02 | 1976-02-10 | J Esposito | Latex stimulant and method of use |
| GB1508495A (en) * | 1975-06-06 | 1978-04-26 | British Petroleum Co | Spraying method |
-
1986
- 1986-12-10 GB GB8719970A patent/GB2194226B/en not_active Expired - Fee Related
- 1986-12-10 BR BR8607066A patent/BR8607066A/en unknown
- 1986-12-10 AU AU68902/87A patent/AU6890287A/en not_active Abandoned
- 1986-12-10 WO PCT/US1986/002636 patent/WO1987004047A1/en unknown
- 1986-12-19 CA CA000525892A patent/CA1282977C/en not_active Expired - Lifetime
- 1986-12-29 TR TR18/87A patent/TR22763A/en unknown
- 1986-12-29 CN CN198686108939A patent/CN86108939A/en active Pending
- 1986-12-29 ZA ZA869743A patent/ZA869743B/en unknown
- 1986-12-30 EG EG805/86A patent/EG17951A/en active
-
1990
- 1990-12-24 AU AU68484/90A patent/AU6848490A/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103596433A (en) * | 2012-02-27 | 2014-02-19 | 生态研究所公司 | Use of a herbicidal composition for controlling parasitic plants |
| CN103596433B (en) * | 2012-02-27 | 2015-05-20 | 生态研究所公司 | Use of a herbicidal composition for controlling parasitic plants |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1987004047A1 (en) | 1987-07-16 |
| BR8607066A (en) | 1988-02-23 |
| CA1282977C (en) | 1991-04-16 |
| GB2194226B (en) | 1990-02-07 |
| TR22763A (en) | 1988-06-21 |
| AU6848490A (en) | 1991-03-14 |
| ZA869743B (en) | 1987-08-26 |
| GB2194226A (en) | 1988-03-02 |
| GB8719970D0 (en) | 1987-09-30 |
| AU6890287A (en) | 1987-07-28 |
| EG17951A (en) | 1991-08-30 |
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