阅读说明：本技术 在高剪切条件下稳定聚丙烯酰胺共聚物溶液的添加剂 (Additive for stabilizing polyacrylamide copolymer solutions under high shear conditions ) 是由 T·H·安德逊 D·A·奥斯特 M·隆 于 2019-10-08 设计创作，主要内容包括：本公开提供了用于稳定水合聚丙烯酰胺共聚物在高剪切条件下改变水溶液的物理性质的能力的组合物和方法。所述组合物通常包含水溶液,所述水溶液包括至少一种水合聚丙烯酰胺共聚物；和至少一种添加剂,所述添加剂选自由以下组成的组：i)具有式1的式的组分,其中式1是R-1-O-EO-a-PO-b-EO-c-PO-d-R-2,其中R-1是氢或任何C-1至C-(18)碳或碳链；O是氧,EO-a是–(CH-2CH-2-O)-a,其中a可以是0至500；PO-b是–(CH(CH-3)CH-2-O)-b,其中b可以是0至70；EO-c是–(CH-2CH-2-O)-c,其中c可以是0至150；PO-d为–CH(CH-3)CH-2-O)-d,其中d是0至30；并且R-2是氢或任何C-1至C-(18)碳或碳链；ii)四官能嵌段共聚物；iii)聚乙烯吡咯烷酮(PVP)均聚物；和iv)其任何组合。(The present disclosure provides methods for stabilizing a hydrated polyacrylamide copolymer for altering water solubility under high shear conditionsCompositions and methods for the ability of physical properties of liquids. The composition generally comprises an aqueous solution comprising at least one hydrated polyacrylamide copolymer; and at least one additive selected from the group consisting of: i) a component having the formula of formula 1, wherein formula 1 is R 1 ‑O‑EO a ‑PO b ‑EO c ‑PO d ‑R 2 Wherein R is 1 Is hydrogen or any C 1 To C 18 Carbon or carbon chain; o is oxygen, EO a Is- (CH) 2 CH 2 ‑O) a Wherein a may be 0 to 500; PO (PO) b Is- (CH) 3 )CH 2 ‑O) b Wherein b may be 0 to 70; EO (ethylene oxide) c Is- (CH) 2 CH 2 ‑O) c Wherein c may be 0 to 150; PO (PO) d is-CH (CH) 3 )CH 2 ‑O) d Wherein d is 0 to 30; and R is 2 Is hydrogen or any C 1 To C 18 Carbon or carbon chain; ii) a tetrafunctional block copolymer; iii) polyvinylpyrrolidone (PVP) homopolymer; and iv) any combination thereof.)

1. A composition, comprising:

A) a hydrated polyacrylamide homopolymer or copolymer;

B) at least one additive selected from the group consisting of:

i) a component having an average calculated molecular weight of between 350 and 22,000 and having the formula

R₁-O-EO_a-PO_b-EO_c-PO_d-R₂

Wherein R is₁Is hydrogen or any C₁To C₁₈A carbon chain; o is oxygen, EO_aIs- (CH)₂CH₂-O)_aWherein a may be 0 to 500; PO (PO)_bIs- (CH)₃)CH₂-O)_bWherein b may be 0 to 70; EO (ethylene oxide)_cIs- (CH)₂CH₂-O)_cWherein c may be 0 to 150; PO (PO)_dis-CH (CH)₃)CH₂-O)_dWherein d is 0 to 30; and R is₂Is hydrogen or any C₁To C₁₈A carbon chain;

ii) a tetrafunctional block copolymer;

iii) polyvinylpyrrolidone (PVP) homopolymer; and

iv) any combination thereof; and

C) an aqueous solution.

2. The composition of claim 1, wherein the average calculated molecular weight of formula 1 is between 400 and 8,000.

3. The composition of claim 1, wherein the tetrafunctional block copolymer has an average calculated molecular weight between 4,000 and 30,000.

4. The composition of claim 1, wherein the tetrafunctional block copolymer has an average calculated molecular weight between 1,000 and 8,000.

5. The composition of claim 1, wherein the PVP homopolymer has a molecular weight between 2,000 and 180,000.

6. The composition of claim 1, wherein the aqueous solution contains at least one agrochemical component.

7. The composition of claim 6, wherein the agrochemical component is a pesticide.

8. The composition of claim 1, wherein the additive is present in an amount of 0.01% to 40% by weight, based on the total weight of the composition.

9. The composition of claim 1, wherein more than one additive is included.

10. A method of forming a composition for reducing the effect of shear on a hydrated polyacrylamide homopolymer or copolymer, the method comprising the step of mixing at least one a-component, at least one B-component, and at least one C-component according to claim 1.

11. A method for reducing the effect of shear on a hydrated polyacrylamide copolymer comprising the step of forming the composition of claim 1 by mixing at least one a-component, at least one B-component, and at least one C-component of the additive with an aqueous solution containing a hydrated polyacrylamide homopolymer or copolymer.

12. The method of claim 12, wherein the droplet size distribution is maintained or increases at a slower rate upon application of shear in a composition comprising an additive of the present disclosure.

13. A method for stabilizing the interaction of long chains of hydrated polyacrylamide homo-or copolymers in an aqueous solution subjected to shear conditions, the method comprising the step of forming the composition according to claim 1 by mixing at least one a-component, at least one B-component and at least one C-component according to claim 1.

14. The method of claim 14, wherein the stable interaction of the long chains of the hydrated polyacrylamide homopolymer or copolymer is evidenced by a slower rate of increase in droplet size distribution.

Background

Hydrated polyacrylamide copolymers are used in many industries to modify the physical properties of aqueous solutions. When these hydrated polyacrylamide copolymers are subjected to high shear environments, their ability to alter the physical properties of aqueous solutions is reduced. In the case of sprayable herbicides, pesticides and fungicides, the hydrated polyacrylamide copolymers are used as anti-drift or drift-reducing agents to prevent the formation of droplets that are too small to control their application within the desired range. However, under shear or high shear conditions, such as those found in spray and pump systems for such compositions, the effectiveness of the hydrated polyacrylamide copolymer may be reduced, allowing the formation of "too small" droplets. When these small droplets are allowed to form, they are susceptible to "drift", thereby bringing them outside the intended application area. This inefficiency is not only that the intended application area does not receive the intended amount of product, but that the drifting droplets may be detrimental to adjacent crops, land and water sources. What is needed is a composition and concomitant method of making using the composition that improves the stability of a hydrated polyacrylamide copolymer under high shear conditions and maintains its ability to change physical properties in aqueous solutions. Further needed are compositions that improve the performance of anti-drift or drift-reducing agents.

Disclosure of Invention

The present disclosure overcomes the problems inherent in the art and provides additives effective in maintaining the ability of hydrated polyacrylamide homopolymers and copolymers to alter the physical properties of aqueous solutions under shear and high shear conditions (collectively "shear"). For purposes of this disclosure, a hydrated polyacrylamide "homopolymer" and a hydrated polyacrylamide "copolymer" shall be used interchangeably, and use of either term shall encompass the other. Advantageously, the additives disclosed herein improve the stability of the hydrated polyacrylamide copolymer, thereby maintaining its properties, even under shear conditions, including high shear conditions. In some forms, shearing is common in agricultural applications. With respect to agrochemicals such as sprayable herbicides, pesticides and fungicides (collectively "pesticides"), control of droplet size and reduction of drift can be achieved by using the additives of the present disclosure in combination with polymers known to modify the water droplet. Thus, such agrochemicals may be applied in appropriate amounts and at appropriate locations to produce the maximum efficiency of the desired application. Some pesticides useful in the present disclosure include, but are not limited to, acetylcholinesterase (AChE) inhibitors, carbamates (e.g., aldicarb), bendiocarb (alanycarb), bendiocarb (benfuracarb), carbosulfan (butocarboxim), butoxycarb (butoxycarb), carbaryl (carbaryl), carbaryl (carbafuran), carbosulfan (carbosulfan), ethiofencarb (ethio-fencarb), fenobucarb (fenobucarb), varacetamidine (formanate), furathiocarb (furathiocarb), isoprocarb (isoprocarb), methiocarb (methiocarb), methomyl (methomyl), metolcarb (methomyl), methiocarb), oxamyl (oxamyl), pirimicarb (oxamyl), carbofuran (dicarb), bendiocarb (carb), methiocarb (methiocarb), methiocarb (carbaryl), methiocarb (methocarb), methiocarb (methocarb), methiocarb (methocarb), and (methocarb), methiocarb), such as, methocarb (methocarb), methiocarb), and (methocarb (, Ethyl bayphos (azinphos-ethyl), azinphos-methyl (az-aminophosph), cadusafos (cadusafos), chlorophosphorus chloride (chlorophenoxyfos), chlorfenapyr (chlorophenvinphos), chlorfenapyr (chlorophenoxyphos), coumaphos (copaphos), cyanophos (cyclophos), demeton-S-methyl, diazinon (diazinon), dichlorvos (dichlorvos)/phosphate, chlorothos (dicroto-phos), dimethoate (dimethoate), methiconate (dimethions), ethisul (diethylphos), fenthion (diethylthiophosphate), Ethion (EPN), prothiophos (EPP), thiothiothiothion (EPP), thiobenzothion (isophos), thion (isophos), thiobenzothion (isophos), thion (isophos-ethyl), thion (isophos), thion (isophos), thiocyanoto (isophos), isophos (isophos), isophos (isop, Isoxathion (isoxathion), malathion (malathion), methidathion (mecarbam), methamidophos (methamidophos), methidathion (methidathion), mephos (mevinphos), monocrotophos (monocrotophos), naled (naled), omethoate (methoate), oxydemethon (methamido-methyl), parathion (parathion), methylparathion (parathion-methyl), phenthoate (phorate), phorate (phosphate), phosmet (phosmet), phosphamidon (phosmet), phosxim (phosmet), diazepam (pipermi-phos-methyl), profenofos (profenos), empenthion (protazos), prothiophos (thion), pyrithion (pyrithion), pyrithion (tetramethon (pyrifos), pyrifos (tetramethon (thion (tetramethon), pyrifos (tetramethon), pyrifos) and tetramethophos), pyrifos (tetramethosup) s (tetramethosup), pyrithion (tetramethosup), pyrifos (tetramethosup), tetrameth, Cyclic dienoic organochlorine compounds (e.g., endosulfan or chlordane), phenylpyrazoles (e.g., ethiprole, fipronil, butenenitrile (flufiprole), pyrazinecarbofipronil and pyriprole), pyrethroid sodium channel modulators (e.g., bifenthrin, allethrin, esbiothrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, prallethrin-bifenthrin, bioallethrin, S-cyclopentenyl bioallethrin, S-cyhalothrin, beta-cyhalothrin, cyfluthrin, cyhalothrin, cyhalo, Cyhalothrin (lambda-cyhalothrin), cyhalothrin (gamma-cyhalothrin), cypermethrin (cypermethrin), alpha-cypermethrin (alpha-cypermethrin), beta-cypermethrin (beta-cypermethrin), theta-cypermethrin (theta-cypermethrin), cypermethrin (zeta-cypermethrin), cyphenothrin (cyphenothrin), deltamethrin (deltamethrin), empenthrin (empenthrin), esfenvalerate (esfenvalerate), etofenprox (etofenprox), fenpropathrin (fenpropathrin), fenvalerate (fenvalerate), fluthrin (flufenvalerate), fluthrin (flufenpropathrin), fluthrin (tau-fluthrin), fenpropathrin (fluthrin), fluthrin (fluthrin), fluthrin (fluthrin, fluthri, Phenothrin (phenothrin), prallethrin (prallethrin), proffluthrin (profluthrin), pyrethrin (pyrethrin) (pyrethrum)), resmethrin (resmethrin), silafluofen (silaflufen), tefluthrin (tefluthrin), kappa-tefluthrin (kappa-tefluthrin), tefluthrin (tetramethythrin), tetramethrin (tetramethrin), tetramethrin (tralomethrin) and transfluthrin (transfluthrin)), sodium channel modulators (e.g., DDT (DDT) or Metroxychron), nicotinic acetylcholine receptor agonists (ChR), neonicotinoids (e.g., acetamiprid), clothianidin (clothianidin), cycloxaprid (epoxypridin), imidacloprid (thiamethoxam), thiamethoxam (1-5-methyl-imidacloprid), thiamethoxam), and thiamethoxam-1- (1-5-2-dihydro-thiamethoxam) -1- (thiamethoxam) -2-thiamethoxam), and thiamethoxam-1-5- (thiamethoxam) -imidacloprid-1-thiamethoxam (2E-) -1- [ (6-chloropyridin-3-yl) methyl ] -N' -nitro-2-pentylenehydrazinecarboximide, 1- [ (6-chloropyridin-3-yl) methyl ] -7-methyl-8-nitro-5-propoxy-1, 2,3,5,6, 7-hexahydroimidazo [1,2-a ] pyridine, nicotine, sulfoxaflor (sulfoxaflor), fluropyrofuranone (flupyradifurone), triflumylpyrimidine (triflumzopyrim), nicotinic acetylcholine receptor allosteric activators, spinosyns (e.g., spinosad) or spinetoram), chloride channel activators from the amamectins and milamemycins (e.g., abamectin), emamectin benzoate (emamectin benzoate), Ivermectin (ivermectin), lepimectin (lepimectin) or milbemectin (milbemectin)), juvenile hormone mimics (e.g., the juvenile hormone analogs methoprene, kinethofenprox (kinethene-imine) and methoprene (methoprene)), fenoxycarb (fenoxycarb), pyriproxyfen (pyriproxyfen), miscellaneous non-specific (multi-site) inhibitors (e.g., alkyl halides such as methyl bromide and other alkyl halides), chloropicrin (chloropirin), sulfuryl fluoride (sulfofuryl fluoride), borax (borax), tartar (tartaric), vertebrate organ TRPV channel regulators (e.g., pymetrozine and fluquine (pyriflunazon)), mite growth inhibitors (e.g., clotezine (clobetamethazine), hexythiazine and flufenpyrum fluoride (flufenazine)), and insect growth inhibitors (e.g., bacillus subtilis) and insect growth inhibitors (bacillus subtilis) and insect growth or spore-producing proteins (spores), such as Bacillus thuringiensis subsp.is-raelensis, Bacillus sphaericus, Bacillus thuringiensis subsp.aizawai, Bacillus thuringiensis subsp.kurstaki, and Bacillus thuringiensis subsp.tenebsonii, or Bt crop protein: cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, and Cry34/35Ab1), mitochondrial ATP synthase inhibitors (e.g., diafenthiuron or organotin acaricides such as azocyclotin (cyclohexanetrin), cyhexatin (cyhexatin), fenbutatin (fenbutatinoxide), propargite (propagite), tetrachlorxasulfone (tetra-difon)), oxidative phosphorylation uncoupling agents via disruption of proton gradients (e.g., chlorfenapyr (chlorfenapyr), DNOC or sulfluramid (sulfluramid)), nicotinic acetylcholine receptor (nar) channel blockers (e.g., nereistoxin analog insecticidal sulfonons bensultap), carbostyroform (thiocyclimide), thiocyclam (thiocyclam), or chlorfluazuron (e.g., chlorfenapyr (chlorfluazuron), thiocycluron inhibitors such as the type 0), or chlorfluazuron (chlorfluazuron), insecticidal compounds such as the class of chlorfenapyr (chlorfenapyr), thiocycluron (chlorfenapyr), thiocyclam), or chlorfenapyr (thiocycluron (e) inhibitors such as the class 0, or chlorflufenoxauron (chlorfenapyr), or chlorfenapyr (chlorfenapyr) or chlorfenapyr (e, for example, or chlorfenapyr (e, Hexaflumuron (hexaflumuron), lufenuron (lufenuron), novaluron (novaluron), noviflumuron (noviflumuron), teflubenzuron (teflubenzuron) or triflumuron (triflumuron)), chitin biosynthesis inhibitors of type 1 (e.g. buprofezin (buprofen)), molting disrupters (e.g. dipropionazide (Dipteran) or cyromazine)), ecdysone receptor agonists (e.g. diacylhydrazines including methoxyfenozide (methoxyfenozide), tebufenozide (tebufenozide), halofenozide (halofenozide), dinotefuran (furazozide) or chromafenozide (chromofenozide)), octopamine receptor agonists (e.g. amitraz)), mitochondrial complex electron transport inhibitors (e.g. hydramethylhydrazone (drazinone), cyfluquinate (fenamate), fenaminoquinone (e.g. mefenozide (mefenozide), e.g. fenaminoquinone (mefenozide (e.g. mefenozide), e.g. mefenozide (mefenozide), e-e.g. mefenozide (mefenozide), e-e, Fenpyroximate (fenpyroximate), pyriminofen (pyrimidifen), pyridaben (pyridaben), tebufenpyrad (tebufenpyrad) or tolfenpyrad (tolfen-pyrad), or rotenone (rotenone)), a voltage-dependent sodium channel blocker (e.g., indoxacarb (indoxacarb), metaflumizone (metaflumizone), 2- [2- (4-cyanophenyl) -1- [3- (trifluoromethyl) phenyl ] ethylidene ] -N- [4- (difluoromethoxy) phenyl ] methylene ] -hydrazine carboxamide or N- (3-chloro-2-methylphenyl) -2- [ (4-chlorophenyl) [4- [ methyl (methylsulfonyl) amino ] phenyl ] methylene ] -hydrazine carboxamide), acetyl-coenzyme carboxylase inhibitors (e.g., tetronic acid and tetramic acid derivatives, for example spirodiclofen (spirodiclofen), spiromesifen (spiromesifen), spirotetramat (spirotetramat) or spiropiperadione (spiroperidion)), mitochondrial complex IV electron transport inhibitors (for example, phosphine such as aluminum phosphide, calcium phosphide, hydrogen phosphide, zinc phosphide, or cyanide), mitochondrial complex II electron transport inhibitors (for example, β -ketonitrile derivatives such as cyenopyrafen or cyflumetofen), diamide ryanodine receptor modulators (for example, flubendiamide (flubendiamide), chloramide (chlor chloaniliprole), cyantraniliprole (cyantraniliprole), flucyanamide (traniliprole), (R) -3-chloro-N1- { 2-methyl-4- [1,2, 2-tetrafluoro-1- (trifluoromethyl) ethyl ] phenyl } -N- (2-methyl) -2-sulfometyl) ethyl } -2, (S) -3-chloro-N1- { 2-methyl-4- [1,2,2, 2-tetrafluoro-1- (trifluoromethyl) ethyl ] phenyl } -N2- (1-methyl-2-methylsulfonylethyl) phthalamide, cyclic bromodiamide (cyclaniliprole), methyl-2- [3, 5-dibromo-2- ({ [ 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazol-5-yl ] carbonyl } amino) benzoyl ] -1, 2-dimethylhydrazine carboxylate, N- [4, 6-dichloro-2- [ (diethyl-lambda-4-sulfonamido) -carbamoyl ] -phenyl ] -2- (3-chloro-2-pyridinyll ) -5- (trifluoromethyl) pyrazole-3-carboxamide, N- [ 4-chloro-2- [ (diethyl- λ -4-sulfonamido) carbamoyl ] -6-methyl-phenyl ] -2- (3-chloro-2-pyridinyl) -5- (trifluoromethyl) pyrazole-3-carboxamide; m.28.5c), N- [ 4-chloro-2- [ (di-2-propyl-. lamda. -4-sulfenyl) carbamoyl ] -6-methyl-phenyl ] -2- (3-chloro-2-pyridyl) -5- (trifluoromethyl) pyrazole-3-carboxamide, N- [4, 6-dichloro-2- [ (di-2-propyl-. lamda. -4-sulfenyl) carbamoyl ] -phenyl ] -2- (3-chloro-2-pyridyl) -5- (trifluoromethyl) pyrazole-3-carboxamide, N- [4, 6-dibromo-2- [ (diethyl-. lamda. -4-sulfenyl) carbamoyl ] -phenyl ] -2- (3-dibromo-2- [ ] -2- (3-chloro-4-sulfenyl) carbamoyl ] -phenyl ] -2- (3-chloro-2-pyridyl) -chloro-2-pyridinyl) -5- (trifluoromethyl) pyrazole-3-carboxamide, N- [2- (5-amino-1, 3, 4-thiadiazol-2-yl) -4-chloro-6-methylphenyl ] -3-bromo-1- (3-chloro-2-pyridinyl) -1H-pyrazole-5-carboxamide, 3-chloro-1- (3-chloro-2-pyridinyl) -N- [2, 4-dichloro-6- [ [ (1-cyano-1-methylethyl) amino ] carbonyl ] phenyl ] -1H-pyrazole-5-carboxamide, 3-bromo-N- [2, 4-dichloro-6- (methylaminoformyl) phenyl ] -1- (3, 5-dichloro-2-pyridinyl) -1H-pyrazole-5-carboxamide, or N- [ 4-chloro-2- [ [ (1, 1-dimethylethyl) amino ] carbonyl ] -6-methylphenyl ] -1- (3-chloro-2-pyridinyl) -3- (fluoromethoxy) -1H-pyrazole-5-carboxamide, a cyclodalodiamine, a choroidal organ regulator with an undefined target, such as flonicamid (flonicamid), an insecticidally active compound with an unknown or undefined mode of action, such as Afiopyropyrrole (afidopyro-pen), Aforana (afoxolan;), Azadirachtin (azadirachtin), sulfadiazine (amidoflumet), benomyl (benzoximate), brofenflurobiamide (brofenlanilide), brofenpyroximate (brozoproxy-late), chlorfenapyr (chinomethionat), cryolite (cryolite), bithiozole (diclomezotiaz), trichlorofol (dicofol), pyrimethanil (flufenarim), flumetoquin (flumetoquin), fluthiacetone (flunisolfone), flurhexfen (fluhexfon), fluopyram (fluOPyramid), fluralanin (fluralane), tetraaldehyde (metaldehydide), methoxazone (methoxazone), piperonyl butoxide (piperidyl butoxide), pyrourea (fluxuridine), pyriproxyfen (pyriproxyfen), pyrazox (methoxazone), or thiafenoxan (4-2-4-2-4-2-4-2-4-2-4-2-, 4-Dimethylbiphenyl-3-yl) -4-hydroxy-8-oxo-1-azaspiro [4.5] dec-3-en-2-one, 1- [ 2-fluoro-4-methyl-5- [ (2,2, 2-trifluoroethyl) sulfinyl ] phenyl ] -3- (trifluoromethyl) -1H-1,2, 4-triazol-5-amine, or active substances based on Bacillus (Votivo, I-1582), fluoropyrine (flupirtine), fluoroindolizine (fluzaindolizine), 4- [5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4H-isoxazol-3-yl ] -2-methyl-N- (1-oxythiophen-3-yl) benzamide, Fluoroformamide (fluxamide), 5- [3- [2, 6-dichloro-4- (3, 3-dichloroallyloxy) phenoxy ] propoxy ] -1H-pyrazole, 4-cyano-N- [ 2-cyano-5- [ [2, 6-dibromo-4- [1,2,2,3,3, 3-hexafluoro-1- (trifluoromethyl) propyl ] phenyl ] carbamoyl ] phenyl ] -2-methylbenzamide, 4-cyano-3- [ (4-cyano-2-methyl-benzoyl) amino ] -N- [2, 6-dichloro-4- [1,2,2,3,3, 3-hexafluoro-1- (trifluoromethyl) -propyl ] phenyl ] -2-fluorobenzamide, and mixtures thereof, N- [5- [ [ 2-chloro-6-cyano-4- [1,2,2,3,3, 3-hexafluoro-1- (trifluoromethyl) propyl ] phenyl ] carbamoyl ] -2-cyano-phenyl ] -4-cyano-2-methyl-benzamide, N- [5- [ [ 2-bromo-6-chloro-4- [2,2, 2-trifluoro-1-hydroxy-1- (trifluoromethyl) ethyl ] phenyl ] carbamoyl ] -2-cyano-phenyl ] -4-cyano-2-methyl-benzamide, N- [5- [ [ 2-bromo-6-chloro-4- [1,2,2,3,3, 3-hexafluoro-1- (trifluoromethyl) -propyl ] phenyl ] carbamoyl ] -2-cyano-phenyl ] -4-cyano-2-methyl-benzamide, 4-cyano-N- [ 2-cyano-5- [ [2, 6-dichloro-4- [1,2,2,3,3, 3-hexafluoro-1- (trifluoromethyl) -propyl ] phenyl ] carbamoyl ] phenyl ] -2-methyl-benzamide, 4-cyano-N- [ 2-cyano-5- [ [2, 6-dichloro-4- [1,2,2, 2-tetrafluoro-1- (trifluoromethyl) ethyl ] phenyl ] carbamoyl ] phenyl ] -2-methyl-benzamide N- [5- [ [ 2-bromo-6-chloro-4- [1,2,2, 2-tetrafluoro-1- (trifluoromethyl) ethyl ] phenyl ] carbamoyl ] -2-cyano-phenyl ] -4-cyano-2-methyl-benzamide, 2- (1, 3-dioxan-2-yl) -6- [2- (3-pyridyl) -5-thiazolyl ] -pyridine, 2- [6- [2- (5-fluoro-3-pyridyl) -5-thiazolyl ] -2-pyridyl ] -pyrimidine, 2- [6- [2- (3-pyridyl) -5-thiazolyl ] -2-pyridyl ] -pyrimidine, N- [ 2-bromo-6-chloro-4- [1,2,2, 2-dichloro-phenyl ] carbamoyl ] -2-cyano-phenyl ] -4-cyano-2-methyl-benzamide, N- [2- (3-pyridyl) -5-thiazolyl ] -pyridine, n-methylsulfonyl-6- [2- (3-pyridyl) thiazol-5-yl ] pyridine-2-carboxamide, 1- [ (6-chloro-3-pyridyl) methyl ] -1,2,3,5,6, 7-hexahydro-5-methoxy-7-methyl-8-nitroimidazo [1,2-a ] pyridine, 1- [ (6-chloropyridin-3-yl) methyl ] -7-methyl-8-nitro-1, 2,3,5,6, 7-hexahydroimidazo [1,2-a ] pyridin-5-ol, 1-isopropyl-N, 5-dimethyl-N-pyridazin-4-ylpyrazole-4-carboxamide, 1- (1, 2-dimethylpropyl) -N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, N, 5-dimethyl-N-pyridazin-4-yl-1- (2,2, 2-trifluoro-1-methylethyl) pyrazole-4-carboxamide, 1- [1- (1-cyanochloropropyl) ethyl ] -N-ethyl-5-methyl-N-pyridazin-4-ylpyrazole-4-carboxamide, and pharmaceutically acceptable salts thereof, N-ethyl-1- (2-fluoro-1-methylpropyl) -5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, 1- (1, 2-dimethylpropyl) -N, 5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, 1- [1- (1-cyanochloropropyl) ethyl ] -N, 5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, N-methyl-1- (2-fluoro-1-methylpropyl) -5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, processes for their preparation and their use in the treatment of cancer, 1- (4, 4-difluorocyclohexyl) -N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, 1- (4, 4-difluorocyclohexyl) -N, 5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, N- (1-methylethyl) -2- (3-pyridyl) -2H-indazole-4-carboxamide, N-cyclopropyl-2- (3-pyridyl) -2H-indazole-4-carboxamide, N-cyclohexyl-2- (3-pyridyl) -2H-indazole-4-carboxamide, and mixtures thereof, 2- (3-pyridyl) -N- (2,2, 2-trifluoroethyl) -2H-indazole-4-carboxamide, 2- (3-pyridyl) -N- [ (tetrahydro-2-furanyl) methyl ] -2H-indazole-5-carboxamide, methyl 2- [ [2- (3-pyridyl) -2H-indazol-5-yl ] carbonyl ] carbazate, N- [ (2, 2-difluorocyclopropyl) methyl ] -2- (3-pyridyl) -2H-indazole-5-carboxamide, N- (2, 2-difluoropropyl) -2- (3-pyridyl) -2H-indazole-5-carboxamide, and pharmaceutically acceptable salts thereof, 2- (3-pyridinyl) -N- (2-pyrimidinylmethyl) -2H-indazole-5-carboxamide, N- [ (5-methyl-2-pyrazinyl) methyl ] -2- (3-pyridinyl) -2H-indazole-5-carboxamide, ticlopyrazole (tyropyrazoflor), salonane (sarolaner), lotilaner (lotilaner), N- [ 4-chloro-3- [ [ (benzyl) amino ] carbonyl ] phenyl ] -1-methyl-3- (1,1,2,2, 2-pentafluoroethyl) -4- (trifluoromethyl) -1H-pyrazole-5-carboxamide, 2- (3-ethylsulfonyl-2-pyridinyl) -3-methyl-6- (trifluoromethyl) imidazo [4,5-b ] pyridine, 2- [ 3-ethylsulfonyl-5- (trifluoromethyl) -2-pyridyl ] -3-methyl-6- (trifluoromethyl) imidazo [4,5-b ] pyridine, 4- [5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4H-isoxazol-3-yl ] -N- [ (4R) -2-ethyl-3-oxo-isoxazol-4-yl ] -2-methyl-benzamide, 4- [5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4H-isoxazol-3-yl ] -N- [ (4R) -2-ethyl- 3-oxo-isoxazolidin-4-yl ] -2-methyl-benzamide, N- [ 4-chloro-3- (cyclopropylcarbamoyl) phenyl ] -2-methyl-5- (1,1,2,2, 2-pentafluoroethyl) -4- (trifluoromethyl) pyrazole-3-carboxamide, N- [ 4-chloro-3- [ (1-cyanochloropropyl) carbamoyl ] phenyl ] -2-methyl-5- (1,1,2,2, 2-pentafluoroethyl) -4- (trifluoromethyl) pyrazole-3-carboxamide, acylnonanes, benzopyranoxanes, 2-chloro-N- (1-cyanocyclopropyl) -5- [1- [ 2-methyl-5-, (1-cyanocyclopropyl) -5- [1- [ 2-methyl-5-) 1,1,2,2, 2-pentafluoroethyl) -4- (trifluoromethyl) pyrazol-3-yl ] pyrazol-4-yl ] benzamide, oxy-azosulfonyl, [ (2S,3R,4R,5S,6S) -3, 5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl ] N- [4- [1- [4- (trifluoromethoxy) phenyl ] -1,2, 4-triazol-3-yl ] phenyl ] carbamate, [ (2S,3R,4R,5S,6S) -3,4, 5-trimethoxy-6-methyl-tetrahydropyran-2-yl ] N- [4- [1- [4- (trifluoromethoxy) phenyl ] -1,2, 4-triazol-3-yl ] phenyl ] carbamate, [ (2S,3R,4R,5S,6S) -3, 5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl ] N- [4- [1- [4- (1,1,2,2, 2-pentafluoroethoxy) phenyl ] -1,2, 4-triazol-3-yl ] phenyl ] carbamate, [ (2S,3R,4R,5S,6S) -3,4, 5-trimethoxy-6-methyl-tetrahydropyran-2-yl ] N- [4- [1- [4- (1,1,2, 2-pentafluoroethoxy) phenyl ] -1,2, 4-triazol-3-yl ] phenyl ] carbamate, (2Z) -3- (2-isopropylphenyl) -2- [ (E) - [4- [1- [4- (trifluoromethoxy) phenyl ] -1,2, 4-triazol-3-yl ] phenyl ] methylenehydrazino ] thiazolidin-4-one, (2Z) -3- (2-isopropylphenyl) -2- [ (E) - [4- [1- [4- (1,1,2,2, 2-pentafluoroethoxy) phenyl ] -1,2, 4-triazol-3-yl ] phenyl ] methylenehydrazino ] thiazolidin-4-one.

Other pesticides include, but are not limited to, respiratory inhibitors, inhibitors of Qo site complex III (e.g., azoxystrobin (azoxystrobin), pyraclostrobin (coumethoxyxystrobin), pyraclostrobin (coumoxystrobin), dimoxystrobin (dimoxystrobin), enestroburin (enestrobin), enestroburin (fenaminstrobin), fenaminstrobin (fenoxystrobin)/flufenoxastrobin (flufenoxystrobin), fluoxastrobin (fluoxystrobin), kresoxim-methyl (kresoxim-methyl), coumoxystrobin (coumoxystrobin-strobin), metominostrobin (metominostrobin), orysastrobin (orysastrobin), picoxystrobin (picoxystrobin), pyraclostrobin (pyraclostrobin), pyraclostrobin (2-methyl-2- (2-dichlorophenoxy) -2- (2-methyl-2- (2-methyl-2-metominostrobin), metominostrobin (metominostrobin) -2-methyl-2- (2-methyl-2-methyl acetamide), metominostrobin, meto, Pyribencarb (pyribencarb), triclopyr/chlorfenapyr (chlorodincarb), famoxadone (fa-moxadene), fenamidone (fenamidone), methyl-N- [2- [ (1, 4-dimethyl-5-phenyl-pyrazol-3-yl) oxymethyl ] phenyl ] -N-methoxy-carbamate, 1- [2- [ [1- (4-chlorophenyl) pyrazol-3-yl ] oxymethyl ] -3-methyl-phenyl ] -4-methyl-tetrazol-5-one, (Z,2E)5[1- (2, 4-dichlorophenyl) pyrazol-3-yl ] -oxy-2-methoxyimino-N, 3-dimethylpent-3-enamide, (Z,2E)5[1 (4-chlorophenyl) pyrazol-3-yl ] oxy-2-methoxyimino-N, 3-dimethylpent-3-enamide, myo-inositol lyase, diflufenican, or methyl 2- (o- ((2, 5-dimethylphenyl-oxymethyl) phenyl) -3-methoxy-acrylate), inhibitors of the Qi site complex III (e.g., cyazofamid (cyazofamid), indazole (amisulbrom), [ (6S,7R,8R)8 benzyl-3- [ (3-hydroxy-4-methoxypyridine-2-carbonyl) amino ] -6-methyl-4, 9-dioxy-1, 5-dioxan-7-yl ] 2-methylpropionate, or fenpyrazamine (fenpicoamid)), inhibitors of complex II (e.g., benoxanil (benodanil), benzovindiflupyr (benzovindifiupyr), bixafen (bixafen), boscalid (bos-calid), carboxin (carboxin), difuramide (fenfuram), fluopyram (flupyram), flutolanil (flutolanil), fluxapyroxad (fluxapyrox-ad), furamex (furametpyr), iprothiamine (isoflufenamid), isopyramid (isopyrazam), isopyrazam (isopyrazam), mefenapyr (isopyrazol), mefenapyr (mepronil), carboxin (Oxycarboxin), fluxafen (penflufen), flufen (penflufen), thiopyrad (thioflufen), penflufen (2-methyl-2- [ (2-phenoxy) -2-pyraflufen (2-methyl-2-pyrazamide), pyriproxyfen (2-pyraflufen-2-methyl-2-pyraflufen), pyriproxyfen (2-methyl-pyraflufen-2-ethyl), pyriproxyfen (pyraflufen-ethyl), pyraflufen-2-ethyl (pyraflufen-p), pyrimethanil (pyraflufen-2-ethyl, pyraflufen-p-methyl-2-p, pyrazone, pyraflufen-2, pyraflufen-p, pyraflufen-2, pyraflufen-p, pyraflufen 2-enoic acid methyl ester, isoflavone, 2- (difluoromethyl) -N- (1,1, 3-trimethyl-indan-4-yl) pyridine-3-carboxamide, 2- (difluoromethyl) -N- [ (3R) -1,1, 3-trimethyl-4-yl ] pyridine-3-carboxamide, 2- (difluoromethyl) -N- (3-ethyl-1, 1-dimethyl-indan-4-yl) pyridine-3-carboxamide, 2- (difluoromethyl) -N- [ (3R) -3-ethyl-1, 1-dimethyl-indan-4-yl ] pyridine-3-carboxamide 2- (difluoromethyl) -N- (1, 1-dimethyl-3-propyl-indan-4-yl) pyridine-3-carboxamide, 2- (difluoromethyl) -N- [ (3R) -1, 1-dimethyl-3-propyl-indan-4-yl ] pyridine-3-carboxamide, 2- (difluoromethyl) -N- (3-isobutyl-1, 1-dimethyl-indan-4-yl) pyridine-3-carboxamide, or 2- (difluoromethyl) -N- [ (3R) -3-isobutyl-1, 1-dimethyl-indan-4-yl ] pyridine-3-carboxamide, other respiratory inhibitors (e.g., flufenamid (diflumetorim), nitrophenyl derivatives, binapacryl (binapacryl), dicroton (dinocoton), dinocap (dinocap), fluazinam (fluazinam), meptyldinocap (meptyldinocap), pyrimethanzone (ferimzone), organometallic compounds, triphenyltin salts (e.g., triphenyltin acetate, triphenyltin chloride, or triphenyltin hydroxide), ametoctradin (ametocradin), sulfenamide (silthiofam), sterol biosynthesis inhibitors (SBI fungicides), C14 demethylase inhibitors, triazoles (triazoles), azaconazole (azazazole), bitertanol (bitonanol), bromuconazole (bromoule-conazole), cyproconazole (cyproconazole), cycloconazole (difenoconazole), difenoconazole (difenoconazole), flufenacetone (flufenazole), flufenazole (flufenacet), flufenacetone (flufenacet-ethyl (fluconazole), flufenacetone (fluconazole (flufenacetone), flufenacetone (flufenazole), flufenazole (flufenazole), flufenacetone (flufenacetone), flufenacetone (flufenacetone, flufenacetone (flufenacetone), amidazole (imibenconazole), ipconazole (ipconazol), metconazole (metconazol), myclobutanil (myclobutanil), oxpoconazole (oxpoconazole), paclobutrazol (paclobutrazol), penconazole (penconazol), propiconazole (propiconazol), prothioconazole (prothioconazole), simeconazole (simeconazole), tebuconazole (tebuconazole), tetraconazole (tetraconazol), triazolone (triadimifueon), triadimenol (triabendazole), triticonazole (uniconazole), 2(2, 4-difluorophenyl) -1, 1-difluoro-3- (tetrazol-1-yl) -1- [5- [4- (2,2, 2-trifluoroethoxy) phenyl ] -2 pyridyl ] propane-2-pyridyl ] propane-2- (2, 4-difluorophenyl) -1- (1, 1-difluoro-1-yl) -1- [5- [4- (2, 2-trifluoroethoxy) phenyl ] -2-pyridyl ] propane-2, 2-1- (1, 4-difluorophenyl) -1- (1, 5-difluoro-pyridyl) propane-1, 1-methoxy-1-2, 2-difluorophenyl ] -propane-1- (1, 4-difluoro-pyridyl) propane-2, 1,5- (trifluoxazole, 2, 4-difluoro-pyridyl) benzene) - -2-ol, isophtifluconazole (ifentrifluconazole), mehtifluconazole (mefentifluconazole), 2- (chloromethyl) -2-methyl-5- (p-tolylmethyl) -1(1,2, 4-triazol-1-ylmethyl) cyclopentanol, imidazoles (imidizoles), imazalil (imazalil), pefurazoate (pefurazoate), prochloraz (prochloraz), trifluoimidazole (triflumizol), pyrimidines (pyrimidines), pyridines (pyridines), piperazines (piperazines), fenamipridol (fenarimol), pyribenzoxim (pyrifenox), triforine (triforine), [3- (4-chloro-2-fluoro-phenyl) -5- (2, 4-difluorophenyl) isoxazol-4-yl ] - (3-pyridyl) methanol, 14-reductase inhibitor, dimethomorph (deltaldiphenyl) methanol (Delta) Dodemorph (dodemorph), moroxydine acetate (dodemorph-acetate), fenpropimorph (fenpropimorph), tridemorph (tridemorph), fenpropidin (fenpropidin), fluazifop (pilalin), spiroxamine (spirox-amine), 3-ketoreductase inhibitors, fenhexamid (fenhexamid), other sterol biosynthesis inhibitors, chloraximate (chlorphenomizole), nucleic acid synthesis inhibitors, phenylamide or acylamino acid fungicides, benalaxyl (benalaxyl), benalaxyl (benalaxyl-M), chiral xylyl (kiral-axyl), metalaxyl (metalaxyl-M), furosemide (flutolanil), oxadixyl (oxadixyl), other nucleic acid synthesis inhibitors, oxadixyl (mexaxyl), isothiazolinone (fenpropine-acetate), 2- (p-butyl-2-methoxy-p-tolyl-2-hydroxy-5- (2-methoxy-tolyl-5-pyrimethanil), 2- (2-methoxy-2-one), 5- (p-tolyl-fluoro-tolyl-5-amino acid), 2-methoxy-2-one, 5-p-tolyl-one, 5-one, and 5-one, 5-fluoro-2 (4-chlorophenylmethoxy) pyrimidin-4-amine, cell division and cytoskeletal inhibitors, tubulin inhibitors, benalaxyl (benomyl), carbendazim (carbendazim), fuberidazole (fuberidazole), thia-benzimidazole (thia-bendazole), thiophanate-methyl (thiophanate-methyl), 3-chloro-4- (2, 6-difluorophenyl) -6-methyl-5-phenyl-pyridazine, 3-chloro-6-methyl-5-phenyl-4- (2,4, 6-trifluorophenyl) pyridazine, N-ethyl-2- [ (3-ethynyl-8-methyl-6-quinolyl) oxy ] butyramide, N-Ethyl-2- [ (3-ethynyl-8-methyl-6-quinolinyl) oxy ] -2-methylsulfanyl-acetamide, 2- [ (3-ethynyl-8-methyl-6-quinolinyl) oxy ] -N (2-fluoroethyl) butanamide, 2- [ (3-ethynyl-8-methyl-6-quinolinyl) oxy ] -N- (2-fluoroethyl) -2-methoxy-acetamide, 2- [ (3-ethynyl-8-methyl-6-quinolinyl) oxy ] -N-propyl-butanamide, 2- [ (3-ethynyl-8-methyl-6-quinolinyl) oxy ] -2-methoxy-N-propyl- Acetamide, 2- [ (3-ethynyl-8-methyl-6-quinolinyl) oxy ] -2-methylsulfonyl-N-propyl-acetamide, 2[ (3-ethynyl-8-methyl-6-quinolinyl) oxy ] -N- (2-fluoroethyl) -2-methylsulfonyl-acetamide, 4- (2-bromo-4-fluorophenyl) -N- (2-chloro-6-fluorophenyl) -2, 5-dimethyl-pyrazol-3-amine, other cell division inhibitors, diethofencarb (diethofencarb), ethaboxam (ethaboxam), pencycuron (pencycuron), fluopyram (fluopicolide), zoxamide (zoxamide), metrafenone (metrafenone), Pyrrolone (pyriofenone), inhibitors of amino acid and protein synthesis, inhibitors of methionine synthesis, cyprodinil (cyclopodinil), mepanipyrim (mepanipyrim), pyrimethanil (pyrimethanil), inhibitors of protein synthesis, blasticidin-S (blastcidin-S), kasugamycin (kasugamycin), kasugamycin hydrochloride hydrate, milbemycin (mildimycin), streptomycin (streptamycin), oxytetracycline (oxytetracycline), inhibitors of signal transduction, MAP/histidine kinase inhibitors, fluoroimines (fluoroemids), iprodione (iprodione), procymidone (procymidone), vinclozolin (vinclozolin), fludioxonil (fluoroxonil), protein G inhibitors, quinoxyfen (quinoxyfen), inhibitors of lipid and membrane synthesis, inhibitors of phospholipid biosynthesis, fenchloramphenium (fenamiphos), inhibitors of amino acid and protein synthesis, inhibitors of isoprothiolane (isoprothiolane), pyricularia (isoprothiolane), pyrithiobac (isoprothiolane), phosphols (isoprothiolane (isophyton), phosphols (isophyton), phosphol (phosphol), phospho, Pentachloronitrobenzene (quintozene), tetrachloronitrobenzene (tecnazene), tolclofos-methyl, diphenyl, diclofop-methyl (chloroneb), etridiazole (ethidizole), phospholipid biosynthesis and cell wall deposition, dimethomorph (dimethomorph), flumorph (flumorph), mandipropamid (manisopamid), pyrimorph (pyrimorph), benthiavalicarb (benthiavalicarb), iprovalicarb, valienamine (valifenalate), compounds and fatty acids affecting cell membrane permeability, propamocarb (propamocarb), inhibitors of oxysterol binding protein, piperalin oxalate (oxathiprirolin), 2- {3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl ] -1, 3-thiazole-4-yl ] -1, 5-dihydro-1, 5-thiazole-4-yl ] -1, 2-oxazol-5-yl } phenylmethanesulfonate, 2- {3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -acetyl } piperidin-4-yl) 1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } -3-chlorophenylmethanesulfonate, 4- [1- [2- [3- (difluoromethyl) -5-methylpyrazol-1-yl ] acetyl ] -4-piperidinyl ] -N-tetrahydronaphthalen-1-ylpyridine-2-carboxamide, 4- [1- [2- [3, 5-bis (difluoromethyl) pyrazol-1-yl ] acetyl ] -4-piperidinyl ] -N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide, 4- [1- [2- [3- (difluoromethyl) -5- (trifluoromethyl) pyrazol-1-yl ] acetyl ] -4-piperidinyl ] -N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide, 4- [1- [2- [ 5-cyclopropyl-3- (difluoromethyl) pyrazol-1-yl ] acetyl ] -4-piperidinyl ] -N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide, methods of treating cancer, 4- [1- [2- [ 5-methyl-3- (trifluoromethyl) pyrazol-1-yl ] acetyl ] -4-piperidinyl ] -N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide, 4- [1- [2- [5- (difluoromethyl) -3- (trifluoromethyl) pyrazol-1-yl ] acetyl ] -4-piperidinyl ] -N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide, 4- [1- [2- [3, 5-bis (trifluoromethyl) pyrazol-1-yl ] acetyl ] -4-piperidinyl ] -N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide, and pharmaceutically acceptable salts thereof, (4- [1- [2- [ 5-cyclopropyl-3- (trifluoromethyl) pyrazol-1-yl ] acetyl ] -4-piperidinyl ] -N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide, inhibitors with a multi-site action, inorganic active substances, Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, thiocarbamates and dithiocarbamates, ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, organo-zinc, chloro compounds, aminosalicylic acid, chlorothalonil, captafol, Captan (captan), folpet (folpet), dichlorphenol (dichlofluanid), hexachlorobenzene, pentachlorophenol and its salts, phthalides, tolylfluane, guanidines and others, guanidine, dodine (dodine), dodine free base, biguanide salts, biguanide octanoate, biguanide octanoamine triacetate, biguanide octaphenyl sulfonate, dithianon (dithianon), 2, 6-dimethyl-1H, 5H- [1,4] dithiophene [2,3-c:5,6-c' ] dipyrrole-1, 3,5,7(2H, 6H) -tetraone, cell wall synthesis inhibitors, glucan synthesis inhibitors, validamycin (validamycin), polyoxin B (polyoxin B), melanin synthesis inhibitors, pyroquilon (pyroquilon), tricyclazole (tricyclazole), cyclopropamide (carpropamide), dicycyclam (dicycyclam), dicycyclam (dicloromethyl-chloride), dicloromethyl-free base, biguanide salts, bis-octanoate, bis (diglucidide), bis (diguanil, Fenoxanil (fenoxanil), plant defense inducers, benzothiadiazole (acibenzolar-S-methyl), probenazole (probenazole), isothiophene (isotianil), tiadinil (tiadinil), prohexadione-calcium (prohexa-dione-calcium), phosphonate, fosetyl-aluminum, phosphoric acid and salts thereof, calcium phosphonate, potassium or sodium bicarbonate, 4-cyclopropyl-N- (2, 4-dimethoxyphenyl) thiadiazole-5-carboxamide, bronopol (bronopol), fenaminomethylene (chinomethionat), cyflufenamid (cyflufenamid), cyazofamid (cymoxanil), dazomethyl (dazomethyl), imicarb (debarb), diclocyanide (diclocymet), pyridaben (diclofen), difenoconazole), fenpyrone (diclofen), oat difenoconazole (fenflurazoquat), dimethyl-sulfate (nphyl-phosphate), fenpyrane (fenpyrazone), fenpyrazone (benzofenamate), fenpyrazone (fenpyrazone), fenpyrazone (fenpyr-ethyl), fenpyrazone (fenpyrone (fenpyrazone), fenpyrazone (fenpyrazone), fenpyrozone (fenpyroxate (fenpyrazone), fenpyroxate (fenpyroxate, Flufenamide (fluetevover), flusulfamide (fluusfamide), fluorouracil (fluvalin), allergenic protein (harpin), metha-sulfocarb (methacarb), nitrapyrin (nitrapyrin), azoxystrobin (nitrothalopropyl), toprocarb (tolprocarb), copper oxine-copper (oxine-copper), proquinazine (proquinazid), tebufloquine (tebufloquin), phylloxtalam (tecloftalam), triazoxide (triazoxide), N ' - (4- (4-chloro-3-trifluoromethyl-phenoxy) -2, 5-dimethyl-phenyl) -N-ethyl-N-methylmercamidine, N ' (4-fluoro-3-trifluoromethyl-phenoxy) -2, 5-dimethyl-phenyl) -N-ethyl-N-methylmercamidine, N ' - [4- [ [3- [ (4-chlorophenyl) methyl ] -1,2, 4-thiadiazol-5-yl ] oxy ] -2, 5-dimethyl-phenyl ] -N-ethyl-N-methyl-formamidine, N ' - (5-bromo-6-indan-2-oxy-2-methyl-3-pyridyl) -N-ethyl-N-methyl-formamidine, N ' - [ 5-bromo-6- [1- (3, 5-difluorophenyl) ethoxy ] -2-methyl-3-pyridyl ] -N-ethyl-N-methyl-formamidine, N ' - [ 5-bromo-6- (4-isopropylcyclohexyloxy) -2-methyl-3-pyridyl ] -N-ethyl-N-methyl-formamidine -formamidine, N ' [ 5-bromo-2-methyl-6- (1-phenethyloxy) -3-pyridyl ] -N-ethyl-N-methyl-formamidine, N ' - (2-methyl-5-trifluoromethyl-4- (3-trimethylsilyl-propoxy) -phenyl) -N-ethyl-N-methyl-formamidine, N ' - (5-difluoromethyl-2-methyl-4- (3-trimethylsilyl-propoxy) -phenyl) -N-ethyl-N-methyl-formamidine, 2- (4-chloro-phenyl) -N- [4- (3, 4-dimethoxy-phenyl) -isoxazol-5-yl ] -2-propaneamidic acid -2-alkynyloxy-acetamide, 3[5- (4-chlorophenyl) -2, 3-dimethyl-isoxazolidin-3-yl ] -pyridine (pyrisoxazole), 3- [5- (4-methylphenyl) -2, 3-dimethyl-isoxazolin-3-yl ] -pyridine, 5-chloro-1 (4, 6-dimethoxy-pyrimidin-2-yl) -2-methyl-1H-benzimidazole, (Z)3 amino-2-cyano-3-phenyl-2-propenoic acid ethyl ester, tetrazolium pyribamate (picarbrazox), N- [6- [ [ (Z) - [ (1-methyltetrazol-5-yl) -phenylmethylene ] amino ] oxymethyl ] -2-pyridyl ] amino Pentyl formate, but-3-ynyl N- [6- [ [ (Z) - [ (1-methyltetrazol-5-yl) -phenyl-methylene ] amino ] oxymethyl ] -2-pyridyl ] carbamate, 2- [2- [ (7, 8-difluoro-2-methyl-3-quinolyl) oxy ] -6-fluoro-phenyl ] propan-2-ol, 2- [ 2-fluoro-6- [ (8-fluoro-2-methyl-3-quinolyl) oxy ] phenyl ] propan-2-ol, quinoxalin (quinofumelin), 9-fluoro-2, 2-dimethyl-5- (3-quinolyl) -3H 1, 4-benzoxazine, 2- (6-benzyl-2-pyridyl) quinazoline, 2- [6- (3-fluoro-4-methoxyphenyl) -5-methyl-2-pyridyl ] quinazoline, dichlorobenzothiazole (dichlobentizox), N' - (2, 5-dimethyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine, and pyrimidinamine (pyrifenamine).

Other examples of pesticides include, but are not limited to, microbial pesticides with fungicidal, bactericidal, virucidal, and/or plant defense activator activity: parasitic powdery mildew (Ampelomyces quiilis), Aspergillus flavus (Aspergillus flavus), Brevibacterium pullulans (Aureobasidium pullulans), Bacillus altivelis (Bacillus altitudinis), Bacillus amyloliquefaciens (B.amyloliquefaciens), Bacillus megaterium (B.megaterium), Bacillus mojavensis (B.mojavensis), Bacillus mycoides (B.mycoides), Bacillus pumilus (B.pumilus), Bacillus simplex (B.samplex), Bacillus halophilus (B.solisalsi), Bacillus subtilis (B.subtertilis), Bacillus amyloliquefaciens (B.subtiliss. amyloliquefaciens), Candida oleophyla (Candida oleophylla), Dibotrytis (C.saiyana), bacterial canker (Bacillus subtilis), Bacillus subtilis (Bacillus subtilis), Bacillus roseus (Bacillus subtilis), Bacillus subtilis (Bacillus subtilis), Bacillus subtilis (Bacillus subtilis), Bacillus subtilis (Bacillus subtilis), Bacillus subtilis (Bacillus subtilis), Bacillus subtilis, Lysobacter antibioticus (lysobacter antibioticus), lysobacter enzymogenes (l.enzymogenes), meldonium mellea (metschnikowiafractcola), fusarium dicoccus (microdochytrium), chitosanum coccineum (microsphaenopsis cochleariae), muscardine (Muscodor albus), bacillus alvei (Paenibacillus alveii), bacillus adnexatus (Paenibacillus epidothioides), bacillus polymyxa (p.polymyxa), pantoea agglomerans (pantoea vasganensis), Penicillium notatum (Penicillium bioliae), coriolus versicolor (phyllobacterium giganteum), Pseudomonas aeruginosa (Trichoderma virens), Pseudomonas aeruginosa (Trichoderma viride), Trichoderma viride (Trichoderma viride) Trichoderma hamatum (t.harmatum), trichoderma harzianum (t.harzianum), trichoderma polyspora (t.polysporam), trichoderma subspinum (t.stromatus), trichoderma viride (t.virens), trichoderma viride (t.viride), sarcandra glabra (typhyllum phacorrhiza), alternaria nodularis (uloides), Verticillium dahlia (Verticillium hlia), cucurbita peplus flava virus (avirulent strain); biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: hypersensitive protein, giant knotweed (Polygonum cuspidatum) extract; microbial pesticides with insecticidal, acaricidal, molluscicidal and/or nematicidal activity: agrobacterium radiobacter (Agrobacterium radiobacter), Bacillus cereus (Bacillus cereus), Bacillus firmus (B.firmus), Bacillus thuringiensis (B.thuringiensis), Bacillus thuringiensis subspecies (B.thunbergensis sswai), Bacillus thuringiensis subspecies israelensis (B.t.ssp.grandis), Bacillus thuringiensis subspecies kurstaki (B.t.ssp.kurstaki), Bacillus thuringiensis subspecies (B.t.ssp.tenensis), Beauveria bassiana (Beauveria bassiaiana), Beauveria bassiana (B.bryontiii), Burkhakia zeyla (B.t.ssbysonis), Bupleurinibacter sphaericus (B.bayana), Sphaerozobium brunettii (B.bryontii), Spirochaeta (Spirochaeta) active Spirocha virus (Spirochaeta), Spirochaeta virus (Spirochaeta), Sphaerotheca virus (Spirochaeta), Sphaerothecia pseudospodopsis), Sphaeformis (H.v), Sphaerotheca (H.e.e), Sphaeformis (H.g. corn spodoptera), Sphaeformis (Heliothis virens (H.v), Sphaeformis (H.g. sp), Sphaeformis (C.g. Pat. chaeta), Sphaeformis (C., The species corynebacterium heterophilum (heterorhabditis bacteriophora), corynebacterium fumosoroseum (isaria fumosorosea), ceroplastes elongata (lecanicilliumlongispora), sarcoptic muscipula (l.muscarium), metarhizium anisopliae (metarhizium anisopliae), metarhizium anisopliae (m.anisopropyla), moraxella (Nomuraearileyi), paecilomyces fumosus (paecilomyces fumosus), paecilomyces purpureus (p.lisinus), paecilomyces japonicus (p.fusciparum), paecilomyces japonicus (paenibacillus sp), paenibacillus japonicus (p.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp., Streptomyces microflavus (s. microflavus); biochemical pesticides with insecticidal, acaricidal, molluscicidal, pheromone and/or nematicidal activity: l-carvone, citral, acetic acid (E, Z) -7, 9-dodecadien-1-yl ester, ethyl formate, decadienoic acid (E, Z) -2, 4-ethyl ester (pyrister), (Z, Z, E) -7,11, 13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavender spicate, cis-jasmone, 2-methyl-1-butanol, methyl eugenol, methyl jasmonate, (E, Z) -2, 13-octadecadien-1-ol, acetic acid (E, Z) -2, 13-octadecadien-1-ol, (E, Z) -3, 13-octadecadien-1-ol, (R) -1-octen-3-ol, Termite pheromone (pentatermanone), acetic acid (E, Z, Z) -3,8, 11-tetradecatrienyl ester, acetic acid (Z, E) -9, 12-tetradecadien-1-yl ester, (Z) -7-tetradecen-2-one, (Z) -acetic acid-9-tetradecen-1-yl ester, (Z) -11-tetradecenal, (Z) -11-tetradecen-1-ol, Chenopodium ambrosides (Chenopodium ambrosoides) extract, neem oil and Quillaja saponaria extract; microbial pesticides with plant stress reduction, plant growth regulator, plant growth promotion and/or yield enhancing activity: the microorganism may be selected from the group consisting of amazonium amazonense (azospirillumazonanse), azospirillum brasilense (a. brasilense), azospirillum lipolyticum (a. lipoferum), azospirillum irascitum (a. irakense), azospirillum halioti (a. halopraeferens), Bradyrhizobium (Bradyrhizobium) species, Bradyrhizobium ehelii (b.elkanii), Bradyrhizobium sojae (b.japonicum), Bradyrhizobium aquaticum (b.liangense), difenodicus acidovorans (delfiac idovorans), arbuscular mycorrhizal fungi (glorarlacies), Mesorhizobium (Mesorhizobium) species, Rhizobium pisorum biological species (rhizinibacillus), Rhizobium pisorhiza sativa (rhiziumbioshizomorphia.

Further examples of pesticides can be found in many places, including "The Pesticide Manual," 17 th edition, c.macbean, British Crop Protection Council (2015) (The teachings and contents of which are incorporated herein by reference). The pesticide handbook is updated regularly and can be accessed on line on a bcpcdata website.

Net another online database of pesticides can be found on the alanwood. In addition to their beneficial use with agrochemicals, the additives of the present disclosure can be used anywhere a polyacrylamide copolymer is used, as the additives provide protection to the copolymer. These additives hydrate and encapsulate the longer polyacrylamide copolymer chains and maintain, maintain and/or improve their physical properties under shear conditions, thereby making their performance similar to that when not subjected to shear conditions. Those skilled in the art understand that while longer polyacrylamide chains can still degrade from shear, the additives of the present disclosure will cause degradation to occur at a slower rate, thereby maintaining, or improving their physical properties as compared to polyacrylamide chains without the additive but subjected to the same shear conditions.

In one aspect, the present disclosure generally provides an additive for an aqueous solution containing at least one hydrated polyacrylamide copolymer. In a preferred form, the additive is mixed with the aqueous solution containing the hydrated polyacrylamide copolymer before the aqueous solution is subjected to shear or high shear conditions.

In some forms, the additive has a general formula of formula 1:

formula 1: r₁-O-EO_a-PO_b-EO_c-PO_d-R₂

Wherein R is₁And R₂Each independently selected from hydrogen or any C₁To C₁₈Carbon or carbon chain; o is oxygen, EO_aIs- (CH)₂CH₂-O)_aWherein a may be 0 to 500; PO (PO)_bIs- (CH)₃)CH₂-O)_bWherein b may be 0 to 70; EO (ethylene oxide)_cIs- (CH)₂CH₂-O)_cWherein c may be 0 to 150; PO (PO)_dis-CH (CH)₃)CH₂-O)_dWherein d is 0 to 30; and wherein formula 1 has a minimum molecular weight of 350, wherein the molecular weight (and all other molecular weights mentioned in the disclosure herein) is reported as the calculated weight average molecular weight. Preferably, the molecular weight of the additive in this form is between 350 and 22,000, more preferably between 365 and 20,000, still more preferably between 375 and 16,000, even more preferably between 385 and 12,000, and still more preferably between 400 and 8,000. As understood by those skilled in the art, a, b, c and d in formula 1 represent the average number of repeating units. The person skilled in the art knows that the alkoxylated product is a distribution of oligomers.

In some forms, the additive is a tetrafunctional block copolymer. Preferably, the tetrafunctional block copolymer is based on ethylene oxide and propylene oxide. Some representative tetrafunctional block copolymers are initiated with ethylene diamine. In some forms, the tetrafunctional block copolymer may be used as(Fromparkas, N.J.) products from BASF Corporation, Florhampark. The molecular weight of the additive comprising the tetrafunctional block copolymer may be in the range of 400 to 30,000, oneSome common ranges are between 500 to 25,000, 700 to 20,000, 800 to 15,000, 900 to 10,000, and 1,000 to 8,000. In some forms, the ranges are similar to those described above for formula 1. Some embodiments have molecular weights of 1650 and 6800.

In some forms, the additive is a polyvinylpyrrolidone homopolymer (hereinafter "PVP"). Preferably, the molecular weight of PVP is between 2,000 and 180,000. For example, PVP has a molecular weight of 2,000, 4,000, 8,000, 10,000, 12,000, 17,000, 20,000, 24,000, 30,000, 34,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 100,000, 110,000, 120,000, 130,000, 140,000, 150,000, 160,000, 170,000, 180,000, and all ranges and numbers between such examples. Some examples of PVP include(Basff Corp.) products.

The additives of the present disclosure may be mixed together in any combination. For example, the additive may comprise:

A) at least one additive of formula I;

B) at least one tetrafunctional block copolymer additive;

C) at least one PVP additive; and

D) any combination thereof.

Thus, the composition may comprise one or more additives of formula 1, and/or one or more tetrafunctional block copolymer additives, and/or one or more PVP additives, or any mixture thereof.

Typically, the total amount of additives is present in an amount of 0.001% to 40% by weight of the composition. More preferably, the additive is present in an amount of 0.002% to 30%, still more preferably 0.003% to 20%, even more preferably 0.004% to 10%, still more preferably 0.005% to 8%, even more preferably 0.006% to 6%, still more preferably 0.007% to 4%, even more preferably 0.008% to 3%, still more preferably 0.009% to 2%, still more preferably by weightFrom 0.01 to 1%, even more preferably from 0.01 to 0.5%, and still more preferably from 0.01 to 0.25%. It will be appreciated that the amount of additive will depend on the type of additive and the composition and/or aqueous solution of the hydrated polyacrylamide copolymer combined therewith. When the additive has the formula R as described above₁-O-EO_a-PO_b-EO_c-PO_d-R₂Or a tetrafunctional block copolymer, some preferred concentrations include 0.05%, 0.1%, 0.125%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, and 0.5%. When the additive is PVP, some preferred concentrations are less than 0.5%, less than 0.4%, less than 0.3%, less than 0.2%, less than 0.1%, and even less than 0.05%.

It is understood that all percentages and amounts in this disclosure refer to the amount of the component in the final solution sprayed on the intended target.

Typically, the hydrated polyacrylamide copolymer is included in an amount commonly used in agricultural applications. Preferably, the content of the hydrated polyacrylamide copolymer is from 10ppm to 200ppm, more preferably from 20ppm to 180ppm, still more preferably from 30ppm to 160ppm, even more preferably from 40ppm to 140ppm, still more preferably from 45ppm to 120ppm, and most commonly from 50ppm to 100 ppm. All amounts refer to the concentration in the solution sprayed on the intended target.

Typically, the aqueous solution is present in an amount of from 60% v/v to 99.5% v/v, more preferably from 70% v/v to 99.5% v/v, even more preferably from 80% v/v to 99.5% v/v, still more preferably from 90% v/v to 99.5% v/v, or 90% v/v, 91% v/v, 92% v/v, 93% v/v, 94% v/v, 95% v/v, 96% v/v, 97% v/v, 98% v/v, 99% v/v or 99.5% v/v.

In another aspect, the composition of the present disclosure comprises at least one additive as described above, at least one hydrated polyacrylamide copolymer, and an aqueous solution containing at least one pesticide. Typically, the pesticide is present in an amount of 0.001% to 50% wt/wt, more preferably 0.01% to 40% wt/wt, even more preferably 0.025% to 30% wt/wt, still more preferably 0.05% to 20% wt/wt, even more preferably 0.075% to 10% wt/wt, more preferably 0.1% to 7% wt/wt, even more preferably 0.25% to 5% wt/wt, and most typically 0.5% to 3% wt/wt.

In another aspect, a method of forming a composition for reducing the effect of shear on a hydrated polyacrylamide copolymer is provided. The method generally comprises the step of mixing the additives described herein with an aqueous solution containing a hydrated polyacrylamide copolymer to form such a composition. The water containing the hydrated polyacrylamide copolymer may further comprise at least one pesticide. The effect of shear on the hydrated polyacrylamide can be determined by comparing the droplet size distribution of the hydrated polyacrylamide copolymers with and without the additives described herein. Advantageously, the droplet size distribution is more stable when the additive is combined with the hydrated polyacrylamide copolymer, where "more stable" refers to the effect of increasing the droplet size distribution at a faster rate for compositions that do not include the additive. Thus, when the additive is combined with the pesticide solution and the hydrated polyacrylamide copolymer, the droplet size distribution still increases over the width of the range, but at a slower rate than when the additive is not present in the composition.

In another aspect, a method and/or composition for reducing the effect of shear on a hydrated polyacrylamide copolymer is provided. The method generally comprises the steps of: the compositions are formed by mixing the additives described herein with an aqueous solution containing a hydrated polyacrylamide copolymer and then subjecting the compositions thus formed to shear conditions. In some forms, the aqueous solution containing the hydrated polyacrylamide copolymer may further comprise at least one pesticide. In some forms, reducing the effect of shear on the hydrated polyacrylamide copolymer can be determined by the increased or maintained stability of the droplet size formed under shear conditions, where such increased or maintained stability refers to a slower degradation rate compared to the hydrated polyacrylamide copolymer without the additive combination as described herein. Advantageously, the methods and compositions reduce the effects of shear conditions that reduce droplet size, thereby increasing the drift of desired solution components. Such effects are attributed to the increased stability of the hydrated polyacrylamide copolymer due to the addition of additives. In some forms, the hydrated polyacrylamide copolymer is used as an anti-drift agent or drift reduction agent.

In another aspect, a method and/or composition for stabilizing long chain interactions of a hydrated polyacrylamide copolymer in an aqueous solution subjected to shear conditions is provided. The method generally comprises the steps of: the compositions are formed by mixing the additives described herein with an aqueous solution containing a hydrated polyacrylamide copolymer and then subjecting the compositions thus formed to shear conditions. In some forms, the aqueous solution containing the hydrated polyacrylamide copolymer may further comprise at least one pesticide. In some forms, the stability of the long chain interactions of the hydrated polyacrylamide copolymer can be determined by the increased or maintained stability of the droplet size formed under shear conditions, where such increased or maintained stability refers to a slower degradation rate compared to the hydrated polyacrylamide copolymer without the additive combination as described herein. Advantageously, the methods and compositions reduce the effects of shear conditions that reduce droplet size, thereby increasing the drift of desired solution components. Such effects are attributed to the increased stability due to the addition of additives to the hydrated polyacrylamide copolymer. In some forms, the hydrated polyacrylamide copolymer is used as an anti-drift agent or drift reduction agent.

In the present disclosure, "co-polymer" and "copolymer" are synonymous.

In the present disclosure, "aqueous solution" refers to ordinary water or a solution containing water.

All drift efficacy tests were conducted according to the united states environmental protection agency's universal validation protocol for pesticide application to row and field crops, reduced spray drift technical tests, as specified in "pesticide spray DRT final universal validation protocol" of 6 months 2016.

Drawings

The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present disclosure. The disclosure may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.

Fig. 1 is a schematic diagram of a pump system for testing compositions of the present disclosure. The system is intended to provide 40psi back pressure for a5 inch centrifugal pump (note-reservoir not shown). The apparatus uses long tubing to provide sliding friction, creating a 40psi back pressure on the pump without increasing nozzle shear. The output at the end of the hose was 1 gallon per minute bypassing 2 gallons per minute (circulation). The only nozzles involved in the shearing process were nozzle atomization for setting in the spray chamber (TeeJet XR8002VS or TeeJet TTI11004 (grendol, illinois, high terra titbit)Science and technology CorpTechnologies,Glendale Heights,IL)))；

FIG. 2 is a graph depicting the results of example 1, showing that when droplet analysis is performed by cycling through the pump system of FIG. 1 multiple times and then spraying through an XR8002VS (Tiger's technologies) nozzle, 3 different polyethylene glycol products having average molecular weights of 400 ("shear additive 1" or "SA 1"), 1450 ("shear additive 2" or "SA 2"), and 8000 ("shear additive 3" or "SA 3") are compared at a 0.25% inclusion level to a 1.7% v/v solution of a 48.7% potassium glycerophosphate herbicide formulation ("PS 1") (e.g., the pesticide solution ROUNDUP(Bayer Crop Science, Inc. (Bayer Crop Science, Research Triangle Park, N.C. (formerly Santa Louis Monsanto, Mo.) of Missouri) and with or without 2 different hydrated polyacrylamide copolymers, namely 1)50ppm of a copolymer of acrylamide monomer, AMPS (2-acrylamido-2-methylpropanesulfonic acid) monomer and a hydrophobic monomer as described in CA2892689A1 (BASF SE) ("PolymerC "or" CP1 "), and 2) the effect of 50ppm of high molecular weight nonionic polyacrylamide (" CP2 ");

fig. 3 is a graph depicting the results of example 2, which shows the effect of 3 different polypropylene glycol products SA4, SA5 and SA6 at 2 different inclusion levels (0.25% for SA4 and SA5, 0.05% for SA 6) with pesticide solution PS1 and addition of CP1 copolymer when subjected to droplet analysis by cycling through the pump system of fig. 1 multiple times and then spraying through an XR8002VS (tiager technologies) nozzle;

FIG. 4 is a graph depicting the results of example 3, which shows the effect of 3 different ethylene oxide propylene oxide block copolymer products SA7, SA8 and SA9 at 0.25% content level with a PS1 pesticide solution and with or without the addition of CP2 hydrated polyacrylamide copolymer when subjected to droplet analysis by cycling through the pump system of FIG. 1 multiple times and then spraying through an XR8002VS (Tiger technologies) nozzle;

FIG. 5 is a graph depicting the results of example 4, which shows the effect of 3 different methoxypolyethylene glycols SA10, SA11, and SA12 at 0.25% content level when subjected to droplet analysis by cycling through the pump system of FIG. 1 multiple times and then spraying through a TTI11004 nozzle (Tiger technologies) at 50ppm of copolymer ("CP 3") with PS1 pesticide solution and with or without the addition of 1 concentration of acrylamide monomer and AMPS (2-acrylamido-2-methylpropane sulfonic acid) monomer;

fig. 6 is a graph depicting the results of example 5, which shows the effect of 5 different alcohol alkoxylates SA13, SA14, SA15, SA16 and SA17 at 0.25% content level with a PS1 pesticide solution and with or without the addition of 1 concentration of hydrated polyacrylamide copolymer polymer CP1, when droplet analysis is performed by cycling through the pump system of fig. 1 multiple times and then spraying through an XR8002VS (tiager technologies) nozzle;

FIG. 7 is a graph depicting the results of example 6, demonstrating 2 different types of droplet analysis when cycled multiple times through the pump system of FIG. 1 and then sprayed through an XR8002VS (Tiger technologies) nozzleAdditive (Basff company)304 and1301 effect with pesticide solution of PS1 at 0.25% content level and with or without addition of 0.625% concentration of hydrated polyacrylamide copolymer CP 1.

FIG. 8 is a series of graphs 8a and 8b depicting the results of example 7, demonstrating that 3 different vinylpyrrolidone homopolymer products SA18, SA19, and SA20 at 0.02% content level when subjected to droplet analysis by cycling through the pump system of scheme 2 of FIG. 1 multiple times and then spraying through a TTI11004 nozzle (Tiger Tech Co., Ltd.) were mixed with PS1, pesticide solution 2 ("PS 2") (which is a 1.1% v/v solution of the 42.8% diglycolamine salt of a dicamba herbicide formulation) (e.g., as in a 1.1% v/v solution of the 42.8% diglycolamine salt of a dicamba herbicide formulation)AndTECHNOLOGY (Bayer crop science, Inc., Trigonoma, N.C.; St. Louis Monsanto, Mo.), or a combination of PS1 and PS2 pesticide solutions with or without 2 concentrations of the hydrated polyacrylamide copolymer polymer CP1 or CP 3.

Detailed Description

The following detailed description and examples set forth preferred materials and procedures for use in accordance with the present disclosure. It should be understood, however, that the description and examples are provided by way of illustration only, and nothing therein should be taken as a limitation on the overall scope of the disclosure.

Example 1

Materials and methods

This example tested the effect of 3 different products shear additive 1(SA1), shear additive 2(SA2) and shear additive 3(SA3) at 0.25% content level with pesticide solution PS1 and with or without 2 different hydrated polyacrylamide copolymers CP1 and CP2 when subjected to droplet analysis by cycling through the pump system of fig. 1 multiple times and then spraying through an XR8002VS (tiager technologies) nozzle. The parameters and results for this example are provided in table 1 below and fig. 2.

TABLE 1

Results

As the data show, without the inclusion of additives, the composition incorporating CP1 exhibited a 21% change in droplet size after 10 passes through the pump system, whereas the droplet size changes were 15% and 13% when 0.25% of SA2 and SA3 were included, respectively. Similarly, the composition incorporating CP2 showed a 28% change in droplet size without the additive, whereas the change in droplet size was only 13% when 0.25% of SA1 was included. Fig. 2 depicts that the additive-containing composition undergoes a smaller change in droplet size, as evidenced by a lower percentage of droplets having a volume of less than 141 μm per continuous pass through the pump system. The droplet size of the pesticide solution alone (without additives) is not affected by the shear conditions.

Example 2

Materials and methods

This example demonstrates the effect of 3 different products SA4, SA5 and SA6 at 2 different content levels (0.25% for SA4 and SA5, 0.05% for SA 6) with pesticide solution PS1 and addition of CP1 copolymer when droplet analysis is performed by cycling through the pumping system of figure 1 multiple times and then spraying through an XR8002VS (tiager technologies) nozzle. The parameters and results for this example are provided in table 2 below and fig. 3.

TABLE 2

As the data and fig. 3 show, without the additives, the composition incorporating CP1 experienced a 21% change in droplet size after 10 passes through the pump system, while the droplet size change was 8% when 0.25% of SA4 was included. When the concentration of CP1 increased to 1%, there was still only an 18% change after 5 pumps. When the concentration of SA6 was reduced to 0.05%, there was only a 26% change over 3 pumps. Fig. 3 also depicts that the additive-containing composition undergoes less droplet size change as evidenced by a lower percentage of droplets having a volume of less than 141 μm per continuous pass through the pump system. The droplet size of the individual pesticide solutions is not affected by the shearing conditions.

Example 3

Materials and methods

This example tested the effect of 3 different products SA7, SA8 and SA9 at 0.25% content level with PS1 and with addition of CP1 hydrated polyacrylamide copolymer when subjected to droplet analysis by cycling through the pump system of figure 1 multiple times and then spraying through an XR8002VS (tiager technologies) nozzle. The parameters and results for this example are provided in table 3 below and fig. 4.

TABLE 3

Results

As shown by the data and figure 4, without the additives, the composition incorporating polymer CP2 underwent a 28% change in droplet size after 10 passes through the pump system, whereas the change in droplet size was 21%, 19% and 27% when 0.25% of SA7, SA8 or SA9 was included. Fig. 4 depicts that the additive-containing composition undergoes less droplet size change as evidenced by a lower percentage of droplets having a volume of less than 141 μm per continuous pass through the pump system. The droplet size of the PS1 pesticide solution alone was not affected by the shear conditions.

Example 4

Materials and methods

This example demonstrates the effect of 3 different methoxypolyethylene glycols SA10, SA11 and SA12 at 0.25% content level when subjected to droplet analysis by cycling through the pump system of fig. 1 multiple times and then spraying through a TTI1104XR8002VS (tiager technologies) nozzle, with a PS1 pesticide solution and with or without the addition of 1 concentration of acrylamide monomer and AMPS (2-acrylamido-2-methylpropanesulfonic acid) monomer ("CP 3"). The parameters and results for this example are provided in table 4 below and fig. 5.

TABLE 4

Results

As the data and figure 5 show, without the additive, the composition incorporating CP3 experienced a 0.18% change in droplet size after 3 passes through the pump system, whereas the changes in droplet size were-0.02%, -0.8%, and 0.07% when 0.25% of SA10, SA11, and SA12 were included, respectively. Fig. 5 also depicts that the additive-containing composition undergoes less droplet size change as evidenced by a lower percentage of droplets having a volume of less than 141 μm per continuous pass through the pump system. The droplet size of the PS1 pesticide solution alone was not affected by the shear conditions.

Example 5

Materials and methods

This example tested the effect of 5 different alcohol alkoxylates SA13, SA14, SA15, SA16 and SA17 at 0.25% content level with PS1 pesticide solution and with or without addition of CP1 copolymer when subjected to droplet analysis by circulation through the pump system of fig. 1 and subsequent nozzle spraying by XR8002VS (tiager technologies). Table 5 and fig. 6 provide the parameters and results for this example.

TABLE 5

Results

As shown by the data and figure 6, without the additive, the composition incorporating CP1 exhibited 21% change in droplet size after 10 passes through the pump system, while the droplet size varied by 21%, 19%, 17%, 12% and 9% when 0.25% of SA13, SA14, SA15, SA16 and SA17 was included. Fig. 6 also depicts that the additive-containing composition undergoes less droplet size change as evidenced by a lower percentage of droplets having a volume of less than 141 μm per continuous pass through the pump system. The droplet size of the PS1 pesticide solution alone was not affected by the shear conditions.

Example 6

Materials and methods

This example tested the effect of 2 different tetrafunctional block copolymers at 0.25% content level with a PS1 pesticide solution with or without 1 concentration of hydrated polyacrylamide copolymer CP1 when subjected to droplet analysis by cycling through the pump system of fig. 1 multiple times and then spraying through an XR8002VS (tiagert technologies) nozzle. The parameters and results for this example are provided in table 6 below and fig. 7.

TABLE 6

Results

As the data and figure 7 show, without the additive, the composition incorporating CP1 exhibited a 21% change in droplet size after 10 passes through the pump system, whereas the droplet size varied by 12% and 20% when including 0.25% Tetronic 304 or Tetronic 1301 (basf corporation), respectively. Fig. 7 further depicts that the additive-containing composition undergoes a small change in droplet size, as evidenced by a lower percentage of droplets having a volume of less than 141 μm per continuous pass through the pump system. The droplet size of the PS1 pesticide solution alone was not affected by the shear conditions.

Example 7

Materials and methods

This example tested the effect of 3 different vinylpyrrolidone products SA18, SA19 and SA20 having average molecular weights of 17,000, 30,000 and 90,000 respectively in combination with a pesticide solution of PS1, PS2, or PS1 and PS2 and with or without the addition of a 0.625% concentration or an 80% concentration of a hydrated polyacrylamide copolymer polymer CP1 or CP3 at a 0.020% content level when subjected to droplet analysis by cycling through the pump system of fig. 1 multiple times and then spraying through the TTI11004 (tiager technologies) nozzle. The parameters and results for this example are provided in table 7 below and in figures 8a and 8 b.

TABLE 7

Results

As the data show, without additives, the composition incorporating polymer CP1 experienced a 1.18% change in droplet size after 10 passes through the pump system, whereas the droplet size changes were 0.84% and 0.32% with the addition of 0.020% SA18 or SA19, respectively. Without additives, polymer CP3 underwent a 1.28% change in droplet size after 10 passes through the pump system of fig. 1, whereas the change in droplet size was 0.47% and 1.23% when SA19 and SA20 were added, respectively. Figures 8a and 8b illustrate that the additive-containing composition undergoes a small change in droplet size, as evidenced by a lower percentage of droplets having a volume of less than 141 μm per continuous pass through the pump system. The droplet size of the individual pesticide solutions is not affected by the shearing conditions.

Discussion of the related Art

The data show that the inclusion of at least one additive of the present disclosure has a surprising effect on the stability of high molecular weight polyacrylamide copolymers in aqueous solution. Stability was demonstrated by comparing droplet size during multiple passes through a pump system that subjects the aqueous solution to high shear conditions. At least one additive may have the formula 1, i.e. R₁-O-EO_a-PO_b-EO_c-PO_d-R₂Wherein R is₁Is hydrogen or any C₁To C₁₈Carbon or carbon chain; o is oxygen, EO_aIs- (CH)₂CH₂-O)_aWhereina may be 0 to 500; PO (PO)_bIs- (CH)₃)CH₂-O)_bWherein b may be 0 to 70; EO (ethylene oxide)_cIs- (CH)₂CH₂-O)_cWherein c may be 0 to 150; PO (PO)_dis-CH (CH)₃)CH₂-O)_dWherein d is 0 to 30; and R is₂Is hydrogen or any C₁To C₁₈Carbon or carbon chain. The at least one additive may also be a tetrafunctional block copolymer. Preferably, the tetrafunctional block copolymer is based on ethylene oxide and propylene oxide. The at least one additive may also be a polyvinylpyrrolidone homopolymer (hereinafter "PVP"). Finally, the additive may comprise any combination of the above additives. In other words, the additive may comprise one or more additives individually and separately selected from the above-mentioned additives. For example, the additive may comprise one or more additives having the formula of formula 1, one or more tetrafunctional block copolymers, and/or one or more PVP additives. Further, the additive may comprise at least one additive of formula 1, and/or at least one tetrafunctional block copolymer, and/or at least one PVP additive.

As the data show, the droplet size of the pesticide solution alone is not affected by the shear conditions. However, the droplet size of a solution that does not include at least one additive is adversely affected because each cycle through the pump system results in a greater change in droplet size than a solution that includes at least one additive as described herein.