CN101103718A - Application of non-dispersive siloxanes surfactant in agricultural chemical composition - Google Patents
Application of non-dispersive siloxanes surfactant in agricultural chemical composition Download PDFInfo
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- CN101103718A CN101103718A CNA2006101032128A CN200610103212A CN101103718A CN 101103718 A CN101103718 A CN 101103718A CN A2006101032128 A CNA2006101032128 A CN A2006101032128A CN 200610103212 A CN200610103212 A CN 200610103212A CN 101103718 A CN101103718 A CN 101103718A
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Abstract
The invention provided a non-dispersive siloxane surfactant of the following formula and the use of the siloxane surfactant in agricultural chemical composites, wherein the meaning of all the symobles is stated in the manual. R3Si-O-[RR'Si-O-] n-O-SiR3.
Description
Technical field
The present invention relates to a kind of method that improves the agriculturally useful compositions performance, particularly improve the method for the effectiveness under its rain fastness (rainfastness), (run-off) performance that runs off and the low humidity condition, described method realizes by adopting silicone surfactant, described silicone surfactant is reduced to surface tension less than about 30mN/m in its aqueous solution of 0.10%, and without the diffusion of spray solution.
Background technology
Leaf worldwide is widely used in agricultural, industry, travels already and the inhabitation field with insecticide and plant growth regulator.As example, these chemical reagent comprise insecticide, fungicide, weed killer herbicide, plant growth regulator, plant nutrient and other chemicals.These chemicals are applied on to be protected, the plant leaf controlling, kill or regulate by sprinkling usually, but other method for example imbibition rope (rope-wick) to use also be known.Some show contact action (contact action) in these reagent certain, kill, control or regulate the growth of target organism at attachment position.Other chemicals are interior absorptions, transfer to the active position away from attachment position in plant corpus.Also have the existing contact action of some chemicals that systemic action is also arranged.
The surfactant goods are used as in forestry, agricultural and gardening usually and improve the agricultural adjuvant that the agricultural chemicals active component is renderd a service, described active component comprises for example micronutrient, growth regulator, biologic product, and agricultural chemicals, for example weed killer herbicide, fungicide, insecticide, propyl ester miticide and miticide.Surfactant is through being commonly used for dispersant, wetting agent and diffusant, and in the product or the packing of preparation or in bucket mix formulation (tank mix), be used as emulsifier.Prior art is renderd a service the diffusibility of spray solution on blade of grass as surfactant a necessary index.Since the 1940's organic herbicide is developed first, surfactant has been used to improve the weed killer herbicide performance.It is the main cause that adopts surfactant that spray solution is spread on blade of grass always.At No. 1 " weed killer herbicide adjuvant " of U.S. weeds science association monograph series, 1988, in the preface of R.H.Hodgson (editor), clearly expressed this point.It comprises such narration: " experience shows, successful weeds control often relies on uses adjuvant suitably in the weeding spray agent, with guarantee to use uniformly and to the covering of target ".
Weed killer herbicide is prepared with surfactant usually.The organosiloxane surfactant provides the surface tension value that significantly is lower than other conventional surfactant.For example, with the BREAK-THRU of Goldschmidt chemical company of organosiloxane surfactant-for example
The Silwet of S240 or Crompton company
L-77-is used in combination with agricultural chemicals, improved the picked-up of leaf to agricultural chemicals, and thereby has improved the effectiveness of agricultural chemicals in the control weed growth.
Numerous about the research of leaf to the picked-up of weed killer herbicide in, glyphosate is reported in the following document with the research that combines of described silicone surfactant: Field﹠amp; Bishop, Pesticide Science, 1988, the 24 volumes, 55-62 page or leaf; Stevens etc., PesticideScience, 1991, the 33 volumes, 371-82 page or leaf; Gaskin﹠amp; Stevens, PesticideScience, 1993, the 38 volumes, 185-92 page or leaf; And Gaskin﹠amp; Stevens, Pesticide Science, 1993, the 38 volumes, 193-200 page or leaf.Include organic siloxane and award Pesticide Science as exhaustive overview adjuvant, that 160 pieces of lists of references are arranged of agricultural chemicals by Stevens, 1993, the 38 volumes are in the 103-22 page or leaf.This area is generally acknowledged, and trisiloxanes (trisiloxane) alcohol ethoxylate surfactant with no more than about 10 ethylene oxide units can give the agricultural spraying mixture super diffusibility.Term " super diffusibility " refers on hydrophobic surface, and for example on plant leaf, described mixture can extend at least 9 times of diameter that a distilled water can expand.
Super diffusibility has been regarded as the key character of described silicone surfactant, this fact by numerous with improve diffusibility as the patent of main purpose be authorized to confirm.For example, the U.S. Pat Patent 5,558,806 of the U.S. Pat Patent 5,104,647 of Policello and Policello and Murphy is a main purpose with the super diffusivity that maintains organic siloxane/organic surface active agent mixture.
The U.S. Pat 5017216 of Dow Corning discloses the back Herbicidal combinations of emerging that contains the siloxane glycol adjuvant, and it is Me that described adjuvant contains structure
3SiO-SiMeR '-O-SiMe
3Trisiloxane surfactant and the mixture of siloxanes dispersant, wherein R ' is the short-chain polyethers group that has 4.6 ethylene oxide units usually.
WO 89/12394, the WO 99/40785, US 6051533, US6040272 and the EP 0483095 that authorize Monsanto disclose multiple Herbicidal combinations, described composition contains silicone surfactant and other adjuvant, for example wetting agent, oil, diol ester and organic cosurfactant.For the useful silicone surfactant of claiming in these inventions, these inventors disclose very wide range of structures, in these silicone surfactants which those skilled in the art seldom indicated can be advantageously used in the effectiveness that strengthens Herbicidal combinations.Yet the example that uses in these inventions is as Silmet
L77 or Silwet
408 trisiloxanes, they have as Me
3SiO-SiMeR '-O-SiMe
3Typical structure, wherein R ' is-(CH
2)
3-(CH
2CH
2O-)
8-Z, wherein Z is hydrogen or methyl.As well known to those skilled in the art, such trisiloxane surfactant gives its aqueous solution super diffusibility, as long as the polyethers chain length is no more than about 10 ethylene oxide units.Only have that these super dispersive siloxanes are selected to come this invention of example, this fact shows that these inventors are following such conventional wisdom, and promptly the speech enhancing of diffusibility use to(for) the overwhelming majority is a key character of the silicone surfactant serviceability that is used as adjuvant in Herbicidal combinations.
Be well known that equally that to those skilled in the art silicone surfactant can have antagonism to the effectiveness of certain plants kind to weed killer herbicide.Gaskin etc. (Pestic.Sci.1993,38,185-192) show some trisiloxanes ethoxylate (TSE), for example Silwet
L-77 surfactant (can obtain) from Crompton, when comparing with independent use weed killer herbicide, can be to the epidermis infiltration of antiweed to grass.The term antagonism is used to show that treatment effect that weed killer herbicide adds adjuvant is less than as a comparison herbicide treatment effect.This when no rain to the trend of resistance glyphosate to the activity of some species, can by in spray solution, add wetting agent for example glycerine alleviate, disclosed as WO 89/12394.Describedly add the rapid draing that thing has prevented spray solution, and quick-drying situation under the low humidity condition-relative moisture 30% or lower-be recurrent when using super dispersive siloxanes for example.
(Pest.Sci.1993 such as Gaskin, 38,192-200) also studied the antagonism of trisiloxane surfactant with 8 to 40 ethylene oxide units, and found this antagonism reduction when the surfactant that uses ethylene oxide content to increase glyphosate.Yet, the information of the effectiveness under rain fastness, loss behavior or the low humidity condition about this glyphosate composition is not provided.
Also known is that the surfactant with high ethylene oxide group content has the fusing point that is higher than common serviceability temperature, and therefore is not easy to operation in application.Therefore, usually need use under the room temperature adjuvant as liquid.
The BP No.1 that is disclosed on December 1st, 1971 of Dow Corning company, 255,249 disclose the Herbicidal combinations that adopts the siloxane glycol copolymer.Wherein declared the general service of the adjuvant of One's name is legion, as example, described general formula has comprised the structure that existing two organosiloxanes (diorganosiloxane) unit has the alkyl diol siloxane unit again by two siloxane glycol general formulas for this.Give two examples that adopt triazine herbicides and adjuvant and show the herbicide action of enhancing, described adjuvant has 1.8 siloxy units and has the glycol chains of being made up of 12 ethylene oxide units fully.Yet, do not have open information about the effectiveness under rain fastness, loss behavior or the low humidity condition of described Herbicidal combinations.In addition, as well known to those skilled in the art, such surfactant that only has a large amount of ethylene oxide units under low serviceability temperature-for example 45 to 50F-is solid, thereby be not easy to the operation.
Summary of the invention
Now unexpectedly find, use following silicone surfactant to obtain for example the significantly improving of performance of Herbicidal combinations of agrochemical composition, described silicone surfactant is reduced to surface tension less than about 30mN/m in its aqueous solution of 0.1%, and does not improve diffusion.Use the described siloxanes can be in the effectiveness of improving under the situation that does not need extra wetting agent under for example rain fastness, leachability, the low humidity condition, and, they in addition can be used in combination with following cosurfactant, described cosurfactant has reaction to the diffusion of super dispersive siloxanes surfactant, and therefore bigger formulation flexibility is provided.
Also find, under serviceability temperature,, especially can be advantageously used in for example performance of Herbicidal combinations of enhancing agrochemical composition in the liquid, the aqueous solution surface tension being reduced to less than about 30mN/m and not improving the silicone surfactant of its diffusion 0.1%.Use the described siloxanes can be in the performance of improving under the situation that does not need extra wetting agent under effectiveness, rain fastness, leachability, the low humidity condition, and, they also can be used in combination with following cosurfactant, and described cosurfactant has reaction to the diffusion of super dispersive siloxanes surfactant.
An object of the present invention is to provide a kind of method that improves the agrochemical composition performance and do not need extra wetting agent, described performance comprises the effectiveness under rain fastness, leachability, the low humidity condition, described method realizes by adopting silicone surfactant, described silicone surfactant can be reduced to its aqueous solution surface tension of 0.10% less than about 30mN/m, and does not improve diffusibility.Another object of the present invention provides a kind of method that improves the agrochemical composition performance and do not need extra wetting agent, described performance comprises the effectiveness under rain fastness, leachability, the low humidity condition, described method realizes by adopting silicone surfactant, described silicone surfactant is liquid under serviceability temperature, and can in its aqueous solution of 0.10%, surface tension be reduced to less than about 30mN/m, and do not strengthen diffusibility.
The silicone surfactant that can use within the scope of the present invention is based on surfactant polysiloxanes, that contain polyether group, described surfactant structure feature makes it in 0.10% (w/w) of silicone surfactant aqueous solution static surface tension to be reduced to less than about 30mN/m, and does not strengthen its diffusibility.
In the present invention, if 0.10% (w/w) aqueous solution of a kind of silicone surfactant is tested on-chip diffusion area at polypropylene, with the super dispersive siloxanes surfactant of routine-for example the well known to a person skilled in the art super diffusibility surfactant Silwet of typical case
L-77 or Breakthru
S240-compares, and is reduced to 1/10th or lower, then described silicone surfactant is defined as " diffusibility that does not strengthen its 0.10% aqueous solution " or " non-dispersive siloxanes surfactant ".
The static surface tension of 0.10% (w/w) aqueous solution of silicone surfactant can be reduced to less than about 30mN/m and is not strengthened diffusible preferred silicone surfactant and have following formula:
R
3Si-O-[RR’Si-O-]
n-O-SiR
3 (I)
Wherein,
N is 1 to 3,
R is an alkyl with 1 to 6 carbon atom,
R ' is a group-(CH with following structure
2)
m-O-(C
2H
4O)
y(C
2H
3R " O)
z-Z,
Wherein,
M is 2 to 6,
R " be methyl independent of each other, ethyl or phenyl,
Z is hydrogen, the alkyl with 1 to 4 carbon atom, or the acyl group with 2 to 6 carbon atoms,
Y is 6 to 30, and
Z is 0 to 10,
Condition is y and the ratio of z is 1 or bigger, and the total n* (y+z) of the oxyalkylene group in the siloxane polymer (I) is at least 12.
Alkyl R and R " be preferably methyl, the value of m is preferably 3.
Preferred subclass (a) is following silicone surfactant (I), and wherein n is 1, R and R " be methyl, m is 3, and y is 13 to 30, and z is 0 to 2, and is preferred especially 0, and Z is hydrogen, methyl or acetyl group.
Another preferred subclass (b) is following silicone surfactant (I), and wherein n is 2, R and R " be methyl, m is 3, and y is 6 to 20, and z is 0 to 2, and is preferred especially 0, and Z is hydrogen, methyl or acetyl group.
Another preferred subclass (c) is following silicone surfactant (I), and wherein n is 1, R and R " be methyl, m is 3, and y is 8 to 30, and z is 2 to 10, and is preferred especially 2 to 6, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
Another preferred subclass (d) is following silicone surfactant (I), and wherein n is 2, R and R " be methyl, m is 3, and y is 5 to 20, and z is 1 to 6, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
Two or more any mixture in the further preferably preferred subclass (a to d).
Subclass (c) and surfactant (d) have following additional advantage, promptly compare with the material that only contains ethylene oxide unit, the existence of propylene oxide unit tends to reduce the fusing point of silicone surfactant, obtain having the material of required following performance, even described performance be under low serviceability temperature-for example 45 to 50 -also are liquid, therefore make its easy operating in application.
Embodiment
Provided the illustrative examples of siloxanes below with required physical property.These structures provide as typical example, are not intended to limit the scope of the invention:
Me
3SiO-[MeR ' SiO]
1-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
13-HMe
3SiO-[MeR ' SiO]
1.2-OSiMe
3R '-(CH wherein
2)
3-O-(CH
2CH
2O)
12(CH
2CH (CH
3) O-)
3-HMe
3SiO-[MeR ' SiO]
1-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O)
15(CH
2CH (CH
3) O-)
2-MeMe
3SiO-[MeR ' SiO]
1.3-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O)
15(CH
2CH (CH
3) O-)
2-C (O) CH
3
Me
3SiO-[MeR ' SiO]
2-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
9-HMe
3SiO-[MeR ' SiO]
2.2-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O)
8(CH
2CH (CH
3) O-)
2-H
As well known to those skilled in the art, polyoxyalkylene polymers has wide molecular weight distribution, and the subscript that more than provides only refers to average composition.The distribution of different oxyalkylene units can be at random or block.
Above-mentioned silicone surfactant can be by well known to a person skilled in the art method preparation, for example in the presence of platinum catalyst, the allyl deriv of siloxanes by containing Si-H and unsaturated polyalkylene oxide derivative-for example-hydrosilylation reactions prepare.The catalyzer of reaction condition and employing by W.Noll for example at " Chemie und Technologie derSilicone ", second edition, Verlag Chemie, among the Weinheim (1968), B.Marciniec is at " Appl.Homogeneous Catal.Organomet.Compd. ", 1996, in 1,487, or G.C.Davis etc. is in U.S. Pat 5, describe in detail in 204,438.As known in the artly be, contain the siloxanes of Si-H and the hydrosilylation product of unsaturated polyalkylene oxide derivative and may contain excessive unsaturated polyalkylene oxide derivative, or its isomerization product.Same knownly be that linear siloxanes derivative and composition thereof can contain and be up to 10%, preferably less than 5% annular siloxane.
Above-mentioned silicone surfactant can be by introducing-unit of [RR " Si-O-] type and further modification, wherein the implication of R as previously discussed, R " be to have the straight chain of 6 to 30 carbon atoms or the alkyl of band straight chain, described carbon atom also can be replaced by nitrogen-atoms.Preferred R " group is alkyl, aminopropyl and the dimethylaminopropyl with 10 to 18 carbon atoms.The silicone surfactant of modification can be by well known to a person skilled in the art the method preparation, for example at the sodium of equilibrium catalyst-for example, the hydroxide of potassium or tetra-allkylammonium or alkoxide-existence under, by siloxanes (I) with contain-straight chain of [RR " Si-O-] unit or annular siloxane or one or the balanced action preparation of dialkoxy silicane; perhaps; in the presence of acid or base catalyst; the precursor siloxanes by containing Si-H with contain-[RR " Si-O-] siloxanes of unit or balanced action of alkoxy silane, and carry out hydrosilylation with the unsaturated polyalkylene oxide compound subsequently and prepare.
Use above-mentioned non-dispersive siloxanes surfactant to provide and improve the effectiveness of agrochemical composition and the method for rain fastness generally, and reducing the method that runs off from plant, described loss often takes place when using super dispersive siloxanes surfactant.They are used under the unfavorable conditions-for example under the low humidity condition-improve the effectiveness of agrochemical composition, and and do not need other wetting agent.If non-dispersive siloxanes surfactant contains a considerable amount of propylene oxide units in its polyoxyalkylene side chain, then the user also obtains such added advantage, the adjuvant that promptly obtains is liquid under low serviceability temperature, thereby easy operating, and do not need solvent or extra premixed/dissolving.
Non-dispersive siloxanes surfactant of the present invention can advantageously use with multiple agrochemical composition, the composition that for example contains micronutrient, growth regulator, agricultural chemicals, described agricultural chemicals comprise weed killer herbicide, fungicide, insecticide, propyl ester miticide (acaracide) and miticide (miticide).
Particularly advantageous is the composition that is used for containing weed killer herbicide.
Suitable weed killer herbicide is, for example:
Growth regulator, for example
Phenoxy acetic acids, for example 2,4-drip (2,4-D) [(2,4 dichloro benzene oxygen base) acetate];
The phenoxy propionic acid class, for example 2,4-drips propionic acid (Dichlorprop) [(RS)-2-(2,4 dichloro benzene oxygen base) propionic acid], Vi par (Mecoprop) [(RS)-2-(4-chloro-oxy-o-cresyl) propionic acid];
The phenoxybutyhc class, for example 2, the 4-Embutox (2,4-DB) [4-(2,4 dichloro benzene oxygen base) butyric acid];
Benzoic acids, for example dicamba (Dicamba) [3,6-two chloro-o-anisic acids];
Other growth regulator, for example
Fluroxypyr (Fluroxypyr) [4-amino-3,5-two chloro-6-fluoro-2-pyridine ethoxyacetic acids], picloram (Picloram) [4-amino-2,3,5-three chloro-2-carboxylic acids], trichlopyr (Triclopyr) [3,5,6-three chloro-2-pyridine ethoxyacetic acids], Copyralid[3,6-dichloropyridine-2-carboxylic acid];
Pigment inhibitor class, for example
Amrol (Amitrole) [1H-1,2,4-triazole-3-base amine; 3-amino-1H-1,2, the 4-triazole], clomazone (Clomazone) [2-(2-benzyl chloride base)-4,4-dimethyl-1,2-oxazole quinoline-3-ketone; 2-(2-benzyl chloride base)-4,4-dimethyl isoxazole quinoline-3-ketone], fluridone (Fluridone) [1-methyl-3-phenyl-5-(a, a, tolyl between a-three fluoro-) 4-pyridone], norflurazon (Norflurazone) [4-chloro-5-methylamino-2-(a, a, tolyl between a-three fluoro-) pyridazine-3 (2H)-ketone];
Mitosis interfering material (Mitotic disruptor), dinitroaniline for example, for example
Isopropalin (Isopropalin) [4-isopropyl-2,6-dinitro-N, N-dipropyl aniline], oryzalin (Oryzalin) [3,5-dinitro-N4N4-dipropyl sulfanilamide (SN)], pendimethalin (Pendimethalin) [N-(1-ethyl propyl)-2,6-dinitro-3,4-dimethylaniline], prodiamine (Prodiamine) [5-dipropyl amino-a, a, a-three fluoro-4,6-dinitrotoluene (DNT) amine; 2,6-dinitro-N1N1 dipropyl-4-trifluoromethyl-m-phenylenediamine], trefanocide (Trifluralin) [a, a, a-three fluoro-2,6-dinitro-N, N-dipropyl-para-totuidine];
Lipid biosynthesis inhibitor class, for example
Clethodim (Clethodim) [(±)-2-[(E)-3-chloroallyloxyamino imino group] propyl group]-5[2 (ethylmercapto group)-propyl group]-3-hydroxyl hexamethylene-3-ketenes], diclofop-methyl (Diclofop-methyl) [(RS)-2-[4-(2, the 4-dichlorophenoxy) phenoxy group] propionic acid], fenoxaprop-P (Fenoxaprop-ethyl) [(±)-2-[4-(6-chloro-1,3-benzoxazoles-2-base oxygen base) phenoxy group] propionic acid; (±)-2-[4-(5-chlorobenzene and oxazole-2-base oxygen base) phenoxy group] propionic acid], efficient fluazifop (Fluazifop-P-butyl) [(R)-and 2-[4-(5-trifluoromethyl-2-pyridine radicals oxygen base) phenoxy group) propionic acid], haloxyfop-P-methyl (Haloxyfop-methyl) [(RS)-and 2-[4-(3-chloro-5-trifluoromethyl-2-pyridine radicals oxygen base) phenoxy group] propionic acid], quizalofop-ethyl (Quizalofop) [(RS)-and 2[4-(6-chloro-quinoxaline-2-base oxygen base) phenoxy group] propionic acid], sethoxydim (Sethoxydim) [(±)-(EZ)-2-(1-ethoxy imino butyl)-5-[2 (ethylmercapto group)-propyl group]-3-hydroxyl hexamethylene-3-ketenes];
Light compositing inhibitor class:
Triazine and s-triazine, for example
Hexazinone (Hexazinone) [3-cyclohexyl-6-dimethylamino-1-methyl isophthalic acid, 3,4-triazine-2,4 (1H, 3H)-and diketone], piperazine humulone (the Metribuzin) [4-amino-6-tert-butyl group-3-methyl mercapto-1,2,3-triazine-5 (4H)-ketone], atrazine (Atrazine) [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazines-2, the 4-diamines], Simanex (Simazine) [6-chloro-N
2, N
4-diethyl-1,3,5-triazines-2, the 4-diamines], cyanazine (Cyanazine) 2-[4-chloro-6-ethylamino-1,3,5-triazines-2-yl] and amino]-2-methyl propionitrile, prometryn (Prometon) [N
2, N
24-diisopropyl-6-methoxyl group-1,3,5-triazines-2, the 4-diamines], ametryn (Ametryn) [N
2-ethyl-N
4-isopropyl-6-methyl mercapto-1,3,5-triazines-2, the 4-diamines];
Substituted urea class, for example
Diuron (Diuron) [3-(3, the 4-dichlorophenyl)-1,1-dimethyl urea], fluometuron (Fluometuron) [1,1-dimethyl-3-(a, a, tolyl between a-three fluoro-) urea], [3-(3 for lorox (Linuron), the 4-dichlorophenyl)-and 1-methoxyl group-1-methyl urea], tebuthiuron (Tebuthiuron) [1-(the 5-tert-butyl group-1,3,4-thiadiazoles-2-yl)-1, the 3-dimethyl urea];
Uracil, for example
Bromacil (Bromacil) [5-bromo-3-sec-butyl-6-methyluracil], terbacil (Terbacil) [the 3-tert-butyl group-5-chloro-6-methyluracil];
Other light compositing inhibitor, for example
Bentazone (Bentazon) [3-isopropyl-1H-2,1,3-benzothiadiazine-4 (3H)-ketone 2,2-dioxide], desmedipham (Desmedipham) [3 '-phenyl amino formoxyl methoxy phenyl Ethyl formate; 3-phenyl amino formoxyl methoxy phenyl Ethyl formate; 3-ethoxy carbonyl aminophenyl carbanilate], methazole (Methazole) [2-()-4-methyl isophthalic acid, 2,4-oxadiazoline-3,5-diketone], phenmedipham (Phenmedipham) [3-(3-methylbenzene carbamoyloxy) phenylcarbamic acid methyl esters; 3-methoxycarbonyl aminophenyl 3 '-methyl phenyl carbamate], Stam F-34 (Propanil) [3 ', 4 '-two chloro-N-propionyl phenylaminos], pyridate (Pyridate) [6-chloro-3-phenyl pyridazine-4-base S-octylsulfo carbonic ester];
Amino acid synthetic inhibitor class, for example other salt of glyphosate, the multiple pine of sulphur (Sulfosate) and N-((phosphonomethyl)) glycine;
Sulfonylurea, for example
[a-(4 for bensulfuron-methyl (Bensulfuron), 6-dimethoxypyridin-2-base carbamoyl sulfonamides)-ortho-toluic acid], chlorimuronethyl (Chlorimuron) [2-(4-chloro-6-methoxy pyrimidine-2-base carbamoyl sulfonamides) benzoic acid], chlorine sulphur swells (Chlorsulfuron) [1-(2-chlorphenyl sulphonyl)-3-(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-yl) urea], metsulfuron-methyl (Metsulfuron) [2-(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-base carbamoyl sulfonamides) benzoic acid], nicosulfuron (Nicosulfuron) [2-(4,6-dimethoxypyridin-2-base carbamoyl sulfonamides)-N, N-dimethyl nicotinamide; 1-(4,6-dimethoxypyridin base)-3-(3-formyl-dimethylamino-2-pyridine radicals sulphonyl) urea], [2-(4 for primisulfuronmethyl (Primisulfuron), 6-two (difluoro-methoxy) pyrimidine-2--amino formoxyl sulfonamides) benzoic acid], sulfometuronmethyl (Sulfumeturon) [2-(4,6-dimethyl pyrimidine-2-base carbamoyl sulfonamides) benzoic acid; 2-[3-(4,6-dimethyl pyrimidine-2-yl) urea groups sulphonyl] benzoic acid], thifensulfuronmethyl (Thifensulfuron) [3-(4-kethoxy-6-methyl isophthalic acid, 3,5-triazine-2-base carbamoyl sulfonamides) thiophene-2-carboxylic acid], triasulfuron (Triasulfuron) [1-(2-(2-chloroethoxy) phenyl sulphonyl)-3 (4-methoxyl groups-6-methyl isophthalic acid, 3,5-triazine-2-yl) urea], tribenuron-methyl (Tribenuron) [2-(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine-2-base (methyl) carbamoyl sulfonamides) benzoic acid];
Imidazolone type, for example
Miaow oxalic acid (Imazamethabenz) [a kind of product, contain (±)-6-(4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl)-meta-toluic acid, (±)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl)-paratolunitrile], imidazoles nicotinic acid (Imazapyr) [2-(4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl) nicotinic acid], imazaquin (Imazaquin) [(RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl) quinoline-3-carboxylic acid], imazethapyr (Imazethapyr) [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl) nicotinic acid];
Cell membrane interfering material class: Bipyridine compound, for example
Diquat (Diquat) [9,10-dihydro-8a-two azonia phenanthrene; 6, the 7-dihydrodi pyridine is [1,2-a:2 ', 1 '-c] pyrazine-5 also, 8-two cations; 1,1 '-ethylene-2,2 '-bipyridyl], paraquat (Paraquat) [1,1 '-dimethyl-4,4 '-bipyridyl (I)]
Diphenylether, for example
Acifluorfen (Acifluorfen) [5-(a-three fluoro-are to toloxyl for 2-chloro-a, a)-2-nitrobenzoic acid], fomesafen (Fomesafen) [5-(a-three fluoro-are to toloxyl for 2-chloro-a, a)-N-mesyl-2-nitrobenzamide; 5-(a-three fluoro-are to toloxyl for 2-chloro-a, a)-N-methyl sulphonyl-2-nitrobenzamide], the commercial goods is called REFLEX ; Lactofen (Lactofen) [0-(5-(2-chloro-a, a, a-three fluoro-are to toloxyl)-2-nitrobenzene formyl)-the DL-ethyl lactate], Oxyfluorfen (Oxyfluorfen) [2-chloro-a, a, a-three fluoro-are to toloxyl 3-ethyoxyl-4-nitrobenzophenone ether];
Cell wall inhibitor class, for example
Dichlobenil (Dichlobenil) [2, the 6-dichloro-benzonitrile], ixoxaben (Isoxaben) [N-[3-(1-ethyl-1-methyl-propyl)-1,2-oxazole-5-yl]-2,6-dimethoxy benzamide; N-[3-(1-ethyl-1-methyl-propyl)-isoxazole-5-base 1-2,6-dimethoxy benzamide];
Other weed killer herbicide, for example
Glufosinate[4-(hydroxyl (methyl) phosphino-)-DL-high lactamine; DL-high lactamine-4-base-(methyl) phosphinic acids], and Brominal (Bromoxynil) [3,5-two bromo-4-hydroxy benzonitriles; 3,5-two bromo-4-hydroxy phenyl cyaniding things, 2,6-two bromo-4-cyano-phenyl caprylates].
Aryl triazolineone, for example carfentrazone (carfentrazone-ethyl).
Particularly preferred weed killer herbicide is N-((phosphonomethyl)) glycine and salt thereof.
It will be appreciated by those skilled in the art that cosurfactant and helping the use of adjuvant is general custom in bucket mixed spray formulation (spray tank mix), pesticidal preparations and adjuvant intermixture.Therefore, the scope of this patent should be understood to comprise the present invention is used in combination with other adjuvant, described other adjuvant comprises, but be not limited to, surfactant, sticker, wetting agent, solvent, oil, float diffusing controlling agent (drift control agent), buffer, filler, deposition (deposition) auxiliary agent and retention agent, defoamer and antifoaming agent, compatilizer (compatibilty agent), and activity of weeding reinforcing agent, for example ammonium sulfate and nitrogenous fertilizer.When the needs adjuvant has multiple character, the mixture advantageous particularly of other surfactant and these new siloxanes.Cosurfactant can comprise nonionic, cation, anion and zwitterionic surfactant.The example of possible cosurfactant comprises, but be not limited to: alkanolamide, alkylaryl alcoxylates and derivative thereof, alkoxylated amines and derivative thereof, quaternary surfactant, alkoxy quaternary ammonium surfactant and derivative thereof, amine oxide, betain and derivative thereof, contain ethylene oxide, propylene oxide, butylene oxide, styrene oxide or its be the copolymer of combination arbitrarily, alcohol alkoxylates and derivative thereof, branched-chain alcoho alcoxylates and derivative thereof, the alkoxylate acid amides, alkoxylated fatty acid, alkoxy fatty acid ester and oil, glyceride, alkoxylated glyceride, imidazoline and derivative thereof, propoxylation quaternary amine, lignin and derivative thereof (for example lignosulfonates), monoglyceride and two glyceride, alkene sulfonate, phosphate, APG, other silicone surfactant (alkoxylate siloxanes for example, alkylsiloxane, the siloxanes that contains betain and quaternary ammonium group, amino silicone and alkoxylate amino silicone), Isosorbide Dinitrate, ethoxylation dehydrated sorbitol ester, sulfosalt surfactant, sulfosuccinate and derivative thereof, soap, and sarcosinate.According to definition, the term that uses among the present invention " fat " comprises the material that derives from animal and plant.
Except can using with surfactant to the diffusibility low-disturbance of the Herbicidal combinations that contains super dispersive siloxanes surfactant--this situation is disclosed in United States Patent (USP) 5,558,806 and 5,104, in 647, its content includes in this specification by reference--, non-dispersive siloxanes of the present invention also can be advantageously mixes with the surfactant of the super dispersive siloxanes of known antagonism.Such example includes, but are not limited to: the ethoxylated alkylamine (Varonic that produces of Goldschmidt chemical company for example
Surfactant), ethoxylated alkyl quaternary amine and the propoxylation quaternary surfactant (Variquat that produces of Goldschmidt chemical company for example
Surfactant), the ethoxylate of ethoxylated alkyl aryl alcohol and derivative thereof, straight chain and branched-chain alcoho.According to definition, the term alkyl that uses in this patent both can refer to that saturated hydrocarbon chain also can refer to aliphatic unsaturated hydrocarbon.
The inventive method can be used for liquid and solid agrochemical composition.They can be used for the mixed spray formulation of bucket, pesticidal preparations, adjuvant intermixture, and be used for such application: wherein after having used weed killer herbicide, then use silicone surfactant, for example disclosed among US 5985793 and the US5821195, its content is included this specification by reference in.Typical serviceability temperature is about 45 to 100 .
The typical agrochemical formulations that contains non-dispersive siloxanes and effective dose active component can comprise total formulation weight for example 1 to 50%, preferred 2 to 20% siloxanes.
The typical adjuvant preparation that contains non-dispersive siloxanes can comprise about 1 to about 99 weight % siloxanes and 0 to about 99% cosurfactant, preferred about 10 to about 70 weight % siloxanes and 30 to about 90% cosurfactant, preferred about 25 to about 50% siloxanes and 50 to about 75% cosurfactant especially.
Embodiment
The diffusion test
By (model: Forco-OPPB, translucent, make) on the polypropylene screen that 0.10% (w/w) aqueous surfactant solutions of 50 microlitres is applied to standard with micropipette, measure different Solution Diffusion areas by VanLeer.Use and measured solution diffusion diameter and reference area in 90 seconds afterwards.In all tests, use deionized water, and envionmental humidity is remained at least 40%.
Surface tension
All surface tension value all adopt Kruss K12 tensometer, measure by platinum plate method (Wilhelmy plate method).
Material:
Silwet
L-77 and Silwet
The 806th, commercially available super diffusibility trisiloxane surfactant can be from Crompton company, White Plains, and NJ buys.
Break-Thru
S240 and Break-Thru
S278 is commercially available super diffusibility trisiloxane surfactant, can be from Goldschmidt chemical company, and Hopewell, VA. buys.
Sylgard
The 309th, commercially available super diffusibility trisiloxane surfactant can be from DowCorning, Midland, and MI. buys.
Silicone surfactant A is the non-dispersive siloxanes surfactant with following formula structure,
Me
3SiO-[MeR ' SiO]
1.2-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
12.5-H
Silicone surfactant B is the non-dispersive siloxanes surfactant with following formula structure,
Me
3SiO-[MeR ' SiO]
1.2-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
10(CH
2CH (CH
3) O-)
2-H
Silicone surfactant C is the non-dispersive siloxanes surfactant with following formula structure,
Me
3SiO-[MeR ' SiO]-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
20(CH
2CH (CH
3) O-)
5-H
Silicone surfactant D is the non-dispersive siloxanes surfactant with following formula structure,
Me
3SiO-[MeR ' SiO]-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
12.5-H
Silicone surfactant E is the non-dispersive siloxanes surfactant with following formula structure,
Me
3SiO-[MeR ' SiO]
1.2-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
12.5-Me
Silicone surfactant F is the non-dispersive siloxanes surfactant with following formula structure,
Me
3SiO-[MeR ' SiO]
2.1-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
12.5-H
Silicone surfactant G is the non-dispersive siloxanes surfactant with following formula structure,
Me
3SiO-[MeR ' SiO]-OSiMe
3Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
17-H.
Following commercially available weed killer herbicide is used for field experiment:
The general chemical name manufacturer of weed killer herbicide commodity
Roundup
Glyphosate Meng Shan
Sempra
Halosulfuronmethyl Meng Shan
2，4-D AMINE 2，4D Universal Cooperative，
Weed Killer
Inc.
Ally
Metsulfuron-methyl Du Pont
Pursuit
The imazethapyr BASF
The comparison of the organosiloxane weeding adjuvant that table 1. is new and the physico chemical property of existing commercially available adjuvant
| Compound | Static surface tension (Dynes/cm) | Diffusion area (cm 2) | 50 | 60 | 70 |
| Silwet L-77 * | 23.8 | 61.0 | Liquid | Liquid | Liquid |
| Silwet 806 * | 23.6 | 54.3 | Liquid | Liquid | Liquid |
| Break-Thru S240 * | 22.4 | 53.3 | Liquid | Liquid | Liquid |
| Break-Thru S278 * | 22.0 | 54.1 | Liquid | Liquid | Liquid |
| Sylgard 309 * | 23.5 | 58.5 | Liquid | Liquid | Liquid |
| Silicone surfactant A | 25.1 | 1.2 | Solid | Solid | Liquid |
| Silicone surfactant B | 24.2 | 1.6 | Liquid | Liquid | Liquid |
| Silicone surfactant C | 28.2 | 0.7 | Liquid | Liquid | Liquid |
| Silicone surfactant D | 23.8 | 1.4 | Solid | Solid | Liquid |
| Silicone surfactant E | 25.0 | 1.3 | Solid | Solid | Solid |
| Silicone surfactant F | 29.8 | 0.7 | Solid | Solid | Liquid |
| Silicone surfactant G | 29.5 | 0.9 | Solid | Solid | Solid |
All data are picked up from 0.1%v/v solution
*Commercially available super diffusibility trisiloxane surfactant
In the diffusion test, typically super dispersive siloxanes surfactant shows 40cm
2Or bigger diffusion area, and non-dispersive siloxanes surfactant of the present invention shows 4cm
2Or littler diffusion area.Surfactant B and C are the non-dispersive siloxanes surfactant of liquid under 50F and higher serviceability temperature.
Embodiment 1. and the rain fastness of herbicide glyphosate on broad leaved weed
It has been generally acknowledged that the rainfall meeting that is up in 6 hours after handling with commercially available weed killer herbicide Roundup reduces the weeds control rate.Carry out field experiment to assess two kinds of non-dispersive siloxanes adjuvant A and B and Roundup
Performance under the situation of (active component is the isopropyl amine salt of n-(phosphonomethyl) glycine) rainfall after using the short time on broad leaved weed.Weeds are in particular test and plant.The seed of kitchen garden (Portulaca oleracea) is sowed in pilot region, and with field cultivator/rake with its implantation.Experimental design is district's group (randomizedcomplete block) fully at random, has the repetition (three replications of paired plots) (simulate rainy with no rain) in three paired plot at each weed killer herbicide and adjuvant combination.Knapsack sprayer with supply 20 gallon/acre (gal/acre) is used.Use weed killer herbicide after 60 minutes, carry out simulated rainfall (2mm rainfall) with the tractor mounted sprayer of supplying 2139 gallon/acre.Handle after 21 days, by experienced field testing crew visually rank weed killer herbicide performance.
| Weed killer herbicide (rate of application) | The mixed adjuvant of bucket | The control of kitchen garden | (killing) percentage |
| No rain | Rainy | ||
| Roundup (12 ounces/acre) | Do not have | 53 | 12 |
| Roundup (12 ounces/acre) | Silicone surfactant A | 55 | 37 |
| Roundup (12 ounces/acre) | Silicone surfactant B | 62 | 28 |
| Roundup (24 ounces/acre) | Do not have | 82 | 25 |
| Roundup (24 ounces/acre) | Silicone surfactant A | 82 | 55 |
| Roundup (24 ounces/acre) | Silicone surfactant B | 87 | 50 |
All adjuvant rate of application are the 0.1%v/v of spray solution.
Two kinds of silicone surfactants all provide rain fastness for Roundup.Stand after 60 minutes under the situation of 2mm simulated rainfall using weed killer herbicide on the plot, the ratio that adds two kinds of silicone surfactants and the weeds control rate of independent use Roundup in spray solution is greater than 2 times.
Embodiment 2. and the rain fastness of herbicide glyphosate on grassy weed
With commercially available weed killer herbicide Roundup (active component: the isopropyl amine salt of n-(phosphonomethyl) glycine) be sprayed on the wild clump of perennial grass (Bracharia decumbens) individually or with the adjuvant that in spray solution, comprises.Spraying volume is 200 liters/hectare (liter/ha).Use weed killer herbicide after 60 minutes, half of each test plot accepted the simulated rainfall of 2mm.Handle after 30 days, by experienced field testing crew visually rank weed killer herbicide performance.
| The herbicide application rate | Adjuvant | Grass control percentage | |
| No rain | Rainy | ||
| Roundup 2.4 liter/hectare | 0 | 65 | 22 |
| Roundup 2.4 liter/hectare | Break-Thru S240 | 70 | 32 |
| Roundup 2.4 liter/hectare | Silicone surfactant B | 77 | 38 |
All adjuvant rate of application are the 0.1%v/v of spray solution.
Silicone surfactant B has strengthened the rain fastness of Roundup.It has also improved the effectiveness of Roundup under no rain condition condition.The careless control rate of silicone surfactant B is higher than commercially available super dispersive siloxanes surfactant Break-Thru
The careless control rate of S240.
The rain fastness of embodiment 3. and sulfonylurea herbicide
Carry out little plot field experiment, with the rain fastness energy of mensuration non-dispersive trisiloxanes bucket mix formulation adjuvant and sulfonylurea herbicide halosulfuronmethyl, and and the commercially available siloxanes (Break-Thru of the super diffusibility of use
S240) situation contrast.The commercially available herbicide formulations that uses is Sempra.The target weeds are the dense wild clump of the rhizome of nutgrass flatsedge (Cyperus rotundus), 1200 to 1400 plant of per hectare.Four repetitions are arranged in the test.Use Sempra with rate of application in the industry (150 gallons/hectare) and the rate of application of half thereof.The adjuvant rate of application is the 0.1%v/v of spraying mixture.Being 200 liters/hectare with knapsack sprayer by the sprinkling volume uses.Use weed killer herbicide after one hour, half of each plot carried out the simulated rainfall of 6mm with tractor mounted sprayer.Handle after 60 days, by experienced field testing crew visually rank weeds control rate.
| Weed killer herbicide | Bucket mix formulation adjuvant | Rhizome of nutgrass flatsedge control percentage | |
| No rain | Rainy | ||
| Sempra 75 gallons/hectare | Do not have | 63.3 | 38.3 |
| Sempra 75 gallons/hectare | Break-Thru S240 | 73.3 | 63.3 |
| Sempra 75 gallons/hectare | Silicone surfactant B | 85.0 | 68.3 |
| Sempra 150 gallons/hectare | Do not have | 73.3 | 63.3 |
| Sempra 150 gallons/hectare | Break-Thru S240 | 91.7 | 81.7 |
| Sempra 150 gallons/hectare | Silicone surfactant B | 95.0 | 83.3 |
All adjuvant rate of application are the 0.1%v/v of spray solution.
The result shows that the non-dispersive siloxanes adjuvant can strengthen the effectiveness of weed killer herbicide very effectively, and described adjuvant is particularly useful aspect the enhancing rain fastness.In fact, this adjuvant obtains being better than commercially available adjuvant Break-Thru usually
The weeds control rate of S240.
The raising that embodiment 4. auxins, sulfonylureas and imidazolidinone weedicide are renderd a service
Carry out little plot field experiment, with the performance of the weed killer herbicide of assessment siloxanes adjuvant and three kinds of different chemical classifications.The commercially available weed killer herbicide of selecting is 2,4-D, Ally
And Pursuit
Weeds are in particular test and plant.The seed of (Ipomea lacunosa) of will big fruit sesbania (Sesbania exaltata) He Duowa leading a cow is sowed in pilot region and is in strip, and with field cultivator/rake with its implantation.Described weeds grow up when using weed killer herbicide.Experimental design is to have the three district's groups fully at random that repeat.Supplying 20 gallon/acre (gal/acre) with knapsack sprayer uses.Handle after 21 days, by experienced field testing crew visually rank weed killer herbicide performance.
Two kinds of adjuvants have improved the performance of all three kinds of weed killer herbicides on two species one or another kind of.Non-dispersive siloxanes, i.e. silicone surfactant B is at least with commercially available super diffusibility surfactant B reak-Thru
S240 is equally effective.
| Herbicide treatment (rate of application) | Adjuvant | Many low-lying areas control percentage of leading a cow | Big fruit sesbania control percentage |
| 2，4 D (16 ounces/acre) | Do not have | 99 | 22 |
| 2，4 D (16 ounces/acre) | Break-Thru S240 | 99 | 75 |
| 2，4 D (16 ounces/acre) | Silicone surfactant B | 99 | 75 |
| Ally (0.05 ounces/acre) | Do not have | 65 | 15 |
| Ally (0.05 ounces/acre) | Break-Thru S240 | 65 | 87 |
| Ally (0.05 ounces/acre) | Silicone surfactant B | 65 | 93 |
| Pursuit (1.4 ounces/acre) | Do not have | 45 | 0 |
| Pursuit (1.4 ounces/acre) | Break-Thru S240 | 57 | 0 |
| Pursuit (1.4 ounces/acre) | Silicone surfactant B | 55 | 0 |
All adjuvant rate of application are the 0.1%v/v of spray solution.
The performance of adjuvant under low relative humidity that embodiment 5 selectes
Carrying out little plot field experiment in the Arizona State, is the performance of commercially available weed killer herbicide Glyphos under the low relative humidity atmospheric conditions of glyphosate (the isopropyl amine salt of n-(phosphonomethyl) glycine) to assess two kinds of siloxanes adjuvants-be silicone surfactant A and B-and active component.Four repetitions are arranged in test.The target weeds are the wild clump of barnyard grass (Echinochloa crus-galli) and kitchen garden.Barnyard grass is difficult to kill with glyphosate usually.Weed killer herbicide is used separately, perhaps use together with the adjuvant that is contained in the spray solution.Use with the knapsack sprayer that 4 8002 flat fan formulas (flat fan) spray nozzle is housed, described nozzle operation covers 7 feet band (swath) in 30psi.Applied volume is every acre of 20 gallons of spray solution.Coverage is the typical range that industry is used.One day of July of drying that is sprayed at heat is in morning, 11:00 carried out approximately.Temperature is 98F, and relative moisture only is 12%.Use weed killer herbicide after one hour, adopt work in 30psi, per minute discharges about 60 gallons high volume sprayer carries out 2mm on half of each plot simulation heavy showers, sprays thing towards weeds.To the rainfall with weeds is typical tropical shower or desert thunderstorm.Handle after 15 days, by experienced testing crew visually rank weed killer herbicide performance.
| Weed killer herbicide (rate of application) | Adjuvant | Simulated rainfall | Broad-leaved control percentage (kitchen garden) | Narrow leaf control percentage (barnyard grass) |
| Glyphos 0.5 quart/acre | Do not have | Not | 47.5 | 47.5 |
| Glyphos 0.5 quart/acre | Do not have | Be | 27.5 | 20.0 |
| Glyphos 0.5 quart/acre | Silicone surfactant A | Not | 60.0 | 57.5 |
| Glyphos 0.5 quart/acre | Silicone surfactant A | Be | 30.0 | 30.0 |
| Glyphos 0.5 quart/acre | Silicone surfactant B | Not | 75.0 | 75.0 |
| Glyphos 0.5 quart/acre | Silicone surfactant B | Be | 62.5 | 30.0 |
All adjuvant rate of application are the 0.1%v/v of spray solution.
Silicone surfactant A and B can both improve glyphosate control rate to broad leaved weed kitchen garden and grassy weed barnyard grass under these very low humidity environment conditions effectively.Equally, two kinds of adjuvants have all improved the rain fastness of glyphosate.These results clearly illustrate that, defined non-dispersive siloxanes can and not need at very low damp condition to strengthen the performance of glyphosate to grassy weed and broad leaved weed under the situation of wetting agent in this patent.Instruction in the prior art (for example Meng Shan all patent WO 89/12394), super diffusibility trisiloxanes need add wetting agent could be effective under low relative moisture.
Foregoing description of the present invention be intended to the explanation and unrestricted.In the view of those skilled in the art, in the described embodiment multiple change or modification can take place.Need not to deviate from scope of the present invention or purport and can make these changes.
Claims (64)
1. a method that improves the rain fastness of agrochemical composition and do not improve its diffusion comprises the silicone surfactant that adds one or more following formulas of effective dose in described agrochemical composition,
R
3Si-O-[RR’Si-O-]
n-O-SiR
3
Wherein,
N is 1 to 3,
R is an alkyl with 1 to 6 carbon atom,
R ' is that a structure is
-(CH
2)
m-O-(C
2H
4O)
y(C
2H
3R " O)
zThe group of-Z,
Wherein,
M is 2 to 6,
R " be methyl independent of each other, ethyl or phenyl,
Z is hydrogen, the alkyl with 1 to 4 carbon atom, or the acyl group with 2 to 6 carbon atoms,
Y is 6 to 30,
Z is 0 to 10,
Condition is y and the ratio of z is 1 or bigger, and the total n* (y+z) of the oxyalkylene group in the siloxane polymer (I) is at least 12.
2. the process of claim 1 wherein that n is 1, R and R " be methyl, m is 3, and y is 13 to 30, and z is 0 to 2, and Z is hydrogen, methyl or acetyl group.
3. the method for claim 2, wherein z is 0.
4. the process of claim 1 wherein that n is 2, R and R " be methyl, m is 3, and y is 6 to 20, and z is 0 to 2, and Z is hydrogen, methyl or acetyl group.
5. the method for claim 4, wherein z is 0.
6. the process of claim 1 wherein that n is 1, R and R " be methyl, m is 3, and y is 8 to 30, and z is 2 to 10, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
7. the method for claim 6, wherein y is 2 to 6 with the ratio of z.
8. the process of claim 1 wherein that n is 2, R and R " be methyl, m is 3, and y is 5 to 20, and z is 1 to 6, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
9. the method for claim 8, wherein y is 2 to 6 with the ratio of z.
10. the process of claim 1 wherein that described agrochemical composition contains the weed killer herbicide of effective dose.
11. the method for claim 10, wherein said weed killer herbicide are N-((phosphonomethyl)) glycine or its salt.
12. one kind reduce agrochemical composition from the plant loss and do not improve the method for its diffusion, comprise the silicone surfactant that in described agrochemical composition, adds one or more following formulas of effective dose,
R
3Si-O-[RR’Si-O-]
n-O-SiR
3
Wherein,
N is 1 to 3,
R is an alkyl with 1 to 6 carbon atom,
R ' is that a structure is
-(CH
2)
m-O-(C
2H
4O)
y(C
2H
3R " O)
zThe group of-Z,
Wherein,
M is 2 to 6,
R " be methyl independent of each other, ethyl or phenyl,
Z is hydrogen, the alkyl with 1 to 4 carbon atom, or the acyl group with 2 to 6 carbon atoms,
Y is 6 to 30,
Z is 0 to 10,
Condition is y and the ratio of z is 1 or bigger, and the total n* (y+z) of the oxyalkylene group in the siloxane polymer (I) is at least 12.
13. the method for claim 12, wherein n is 1, R and R " be methyl, m is 3, and y is 13 to 30, and z is 0 to 2, and Z is hydrogen, methyl or acetyl group.
14. the method for claim 13, wherein z is 0.
15. the method for claim 12, wherein n is 2, R and R " be methyl, m is 3, and y is 6 to 20, and z is 0 to 2, and Z is hydrogen, methyl or acetyl group.
16. the method for claim 15, wherein z is 0.
17. the method for claim 12, wherein n is 1, R and R " be methyl, m is 3, and y is 8 to 30, and z is 2 to 10, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
18. the method for claim 17, wherein y is 2 to 6 with the ratio of z.
19. the method for claim 12, wherein n is 2, R and R " be methyl, m is 3, and y is 5 to 20, and z is 1 to 6, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
20. the method for claim 19, wherein y is 2 to 6 with the ratio of z.
21. the method for claim 12, wherein said agrochemical composition contains the weed killer herbicide of effective dose.
22. the method for claim 12, wherein said weed killer herbicide are N-((phosphonomethyl)) glycine or its salt.
23. one kind is improved the effectiveness of agrochemical composition under the low humidity condition, do not need wetting agent and is not improved the method for the diffusion of described composition, comprise the silicone surfactant that in described agrochemical composition, adds one or more following formulas of effective dose
R
3Si-O-[RR’Si-O-]
n-O-SiR
3
Wherein,
N is 1 to 3,
R is an alkyl with 1 to 6 carbon atom,
R ' is that a structure is
-(CH
2)
m-O-(C
2H
4O)
y(C
2H
3R " O)
zThe group of-Z,
Wherein,
M is 2 to 6,
R " be methyl independent of each other, ethyl or phenyl,
Z is hydrogen, the alkyl with 1 to 4 carbon atom, or the acyl group with 2 to 6 carbon atoms,
Y is 6 to 30,
Z is 0 to 10,
Condition is y and the ratio of z is 1 or bigger, and the total n* (y+z) of the oxyalkylene group in the siloxane polymer (I) is at least 12.
24. the method for claim 23, wherein n is 1, R and R " be methyl, m is 3, and y is 13 to 30, and z is 0 to 2, and Z is hydrogen, methyl or acetyl group.
25. the method for claim 24, wherein z is 0.
26. the method for claim 23, wherein n is 2, R and R " be methyl, m is 3, and y is 6 to 20, and z is 0 to 2, and Z is hydrogen, methyl or acetyl group.
27. the method for claim 26, wherein z is 0.
28. the method for claim 23, wherein n is 1, R and R " be methyl, m is 3, and y is 8 to 30, and z is 2 to 10, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
29. the method for claim 28, wherein y is 2 to 6 with the ratio of z.
30. the method for claim 23, wherein n is 2, R and R " be methyl, m is 3, and y is 5 to 20, and z is 1 to 6, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
31. the method for claim 30, wherein y is 2 to 6 with the ratio of z.
32. the method for claim 23, wherein said agrochemical composition contains the weed killer herbicide of effective dose.
33. the method for claim 32, wherein said weed killer herbicide are N-((phosphonomethyl)) glycine or its salt.
34. method that improves the effectiveness of agrochemical composition, described composition contains the cosurfactant that is selected from ethoxylated alkylamine, ethoxylated alkyl quaternary amine and propoxylation quaternary surfactant, ethoxylated alkyl aryl alcohol and derivative thereof, straight chain and branched-chain alcoho ethoxylate, described method comprises the silicone surfactant that adds one or more following formulas of effective dose in described agrochemical composition
R
3Si-O-[RR’Si-O-]
n-O-SiR
3
Wherein,
N is 1 to 3,
R is an alkyl with 1 to 6 carbon atom,
R ' is that a structure is
-(CH
2)
m-O-(C
2H
4O)
y(C
2H
3R " O)
zThe group of-Z,
Wherein,
M is 2 to 6,
R " be methyl independent of each other, ethyl or phenyl,
Z is hydrogen, the alkyl with 1 to 4 carbon atom, or the acyl group with 2 to 6 carbon atoms,
Y is 6 to 30,
Z is 0 to 10,
Condition is y and the ratio of z is 1 or bigger, and the total n* (y+z) of the oxyalkylene group in the siloxane polymer (I) is at least 12.
35. the method for claim 34, wherein n is 1, R and R " be methyl, m is 3, and y is 13 to 30, and z is 0 to 2, and Z is hydrogen, methyl or acetyl group.
36. the method for claim 35, wherein z is 0.
37. the method for claim 34, wherein n is 2, R and R " be methyl, m is 3, and y is 6 to 20, and z is 0 to 2, and Z is hydrogen, methyl or acetyl group.
38. the method for claim 37, wherein z is 0.
39. the method for claim 34, wherein n is 1, R and R " be methyl, m is 3, and y is 8 to 30, and z is 2 to 10, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
40. the method for claim 39, wherein y is 2 to 6 with the ratio of z.
41. the method for claim 34, wherein n is 2, R and R " be methyl, m is 3, and y is 5 to 20, and z is 1 to 6, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
42. the method for claim 41, wherein y is 2 to 6 with the ratio of z.
43. the method for claim 34, wherein said agrochemical composition contains the weed killer herbicide of effective dose.
44. the method for claim 43, wherein said weed killer herbicide are N-((phosphonomethyl)) glycine or its salt.
45. a method that improves the effectiveness of agrochemical composition and do not improve its diffusion comprises the silicone surfactant that adds one or more following formulas of effective dose in described agrochemical composition,
R
3Si-O-[RR’Si-O-]
n-O-SiR
3
Wherein,
N is 1 to 3,
R is an alkyl with 1 to 6 carbon atom,
R ' is that a structure is
-(CH
2)
m-O-(C
2H
4O)
y(C
2H
3R " O)
zThe group of-Z,
Wherein,
M is 2 to 6,
R " be methyl independent of each other, ethyl or phenyl,
Z is hydrogen, the alkyl with 1 to 4 carbon atom, or the acyl group with 2 to 6 carbon atoms,
Y is 6 to 30,
Z is 0 to 10,
Condition is y and the ratio of z is 1 or bigger, and the total n* (y+z) of the oxyalkylene group in the siloxane polymer (I) is at least 12.
46. the method for claim 45, wherein
N is 1,
R and R " be methyl,
M is 3,
Y is 8 to 30,
Z is 2 to 10, and
Z is hydrogen, methyl or acetyl group,
And y is 2 to 10 with the ratio of z.
47. the method for claim 46, wherein y is 2 to 6 with the ratio of z.
48. the method for claim 45, wherein n is 2, R and R " be methyl, m is 3, and y is 5 to 20, and z is 1 to 6, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
49. the method for claim 48, wherein y is 2 to 6 with the ratio of z.
50. the method for claim 45, wherein said agrochemical composition contains the weed killer herbicide of effective dose.
51. the method for claim 50, wherein said weed killer herbicide are N-((phosphonomethyl)) glycine or its salt.
52. method that improves the rain fastness of agrochemical composition and do not improve its diffusion, comprise one or more silicone surfactants that in described agrochemical composition, add effective dose, described silicone surfactant has the surface tension less than about 30mN/m in 0.10% the aqueous solution, and the diffusion area on polypropylene surface be equal to or less than following formula super dispersive siloxanes surfactant diffusion area about 10%
Me
3SiO-[MeR’SiO]
1-OSiMe
3
Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
8-Me)
53. one kind reduce agrochemical composition from the plant loss and do not improve the method for its diffusion, comprise one or more silicone surfactants that in described agrochemical composition, add effective dose, described silicone surfactant has the surface tension less than about 30mN/m in 0.10% the aqueous solution, and the diffusion area on polypropylene surface be equal to or less than following formula super dispersive siloxanes surfactant diffusion area about 10%
Me
3SiO-[MeR’SiO]
1-OSiMe
3
Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
8-Me)
54. one kind is improved the effectiveness of agrochemical composition under the low humidity condition, do not need wetting agent and is not improved the method for the diffusion of described composition; Comprise one or more silicone surfactants that add effective dose in the described agrochemical composition; Described silicone surfactant has the surface tension less than about 30mN/m in 0.10% the aqueous solution; And the diffusion area on polypropylene surface be equal to or less than following formula super dispersive siloxanes surfactant diffusion area about 10%
Me
3SiO-[MeR’SiO]
1-OSiMe
3
Wherein R '=-(CH
2)
3-O-(CH
2CH
2O-)
8-Me)
55. contain one or more silicone surfactants and the optional agrochemical composition that contains one or more organic cosurfactants, described composition is liquid under serviceability temperature, and described silicone surfactant has less than the surface tension of about 30mN/m in 0.10% aqueous solution and does not improve its diffusibility, wherein said silicone surfactant has following structural formula
R
3Si-O-[RR’Si-O-]
n-O-SiR
3
Wherein,
N is 1 to 3,
R is an alkyl with 1 to 6 carbon atom,
R ' is that a structure is
-(CH
2)
m-O-(C
2H
4O)
y(C
2H
3R " O)
zThe group of-Z,
Wherein,
M is 2 to 6,
R " be methyl independent of each other, ethyl or phenyl,
Z is hydrogen, the alkyl with 1 to 4 carbon atom, or the acyl group with 2 to 6 carbon atoms,
Y is 6 to 30,
Z is 0 to 10,
Condition is y and the ratio of z is 1 or bigger, and the total n* (y+z) of the oxyalkylene group in the siloxane polymer (I) is at least 12.
56. the agrochemical composition of claim 55, wherein
N is 1,
R and R " be methyl,
M is 3,
Y is 8 to 30,
Z is 2 to 10, and
Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
57. the agrochemical composition of claim 56, wherein y is 2 to 6 with the ratio of z.
58. the agrochemical composition of claim 55, wherein n is 2, R and R " be methyl, m is 3, and y is 5 to 20, and z is 1 to 6, and Z is hydrogen, methyl or acetyl group, and the ratio of y and z is 2 to 10.
59. the agrochemical composition of claim 58, wherein y is 2 to 6 with the ratio of z.
60. the agrochemical composition of claim 55, wherein said agrochemical composition contains the weed killer herbicide of effective dose.
61. the agrochemical composition of claim 60, wherein said weed killer herbicide are N-((phosphonomethyl)) glycine or its salt.
62. the agrochemical composition of claim 55, wherein said composition contain one or more non-dispersive siloxanes surfactants of 1 to 50 weight %.
63. the composition of claim 55, wherein said composition contain one or more non-dispersive siloxanes surfactants of 10 to 70 weight % and one or more organic cosurfactants of 30 to 90 weight %.
64. the composition of claim 63, wherein said organic cosurfactant is selected from ethoxylated alkylamine, ethoxylated alkyl quaternary amine and propoxylation quaternary surfactant, ethoxylated alkyl aryl alcohol and derivative thereof, straight chain and branched-chain alcoho ethoxylate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101032128A CN101103718A (en) | 2006-07-14 | 2006-07-14 | Application of non-dispersive siloxanes surfactant in agricultural chemical composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101032128A CN101103718A (en) | 2006-07-14 | 2006-07-14 | Application of non-dispersive siloxanes surfactant in agricultural chemical composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101103718A true CN101103718A (en) | 2008-01-16 |
Family
ID=38997964
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101032128A Pending CN101103718A (en) | 2006-07-14 | 2006-07-14 | Application of non-dispersive siloxanes surfactant in agricultural chemical composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101103718A (en) |
-
2006
- 2006-07-14 CN CNA2006101032128A patent/CN101103718A/en active Pending
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