CN109641814A - Non-corrosive nitrification inhibitor polar solvent preparation - Google Patents

Non-corrosive nitrification inhibitor polar solvent preparation Download PDF

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Publication number
CN109641814A
CN109641814A CN201680074961.4A CN201680074961A CN109641814A CN 109641814 A CN109641814 A CN 109641814A CN 201680074961 A CN201680074961 A CN 201680074961A CN 109641814 A CN109641814 A CN 109641814A
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China
Prior art keywords
preparation
pyridine
trichloromethyl
chloro
dimethyl
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CN201680074961.4A
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CN109641814B (en
Inventor
H·戴夫
L·刘
A·威廉姆斯
R·戈亚尔
N·菲也特
C·莫罗
S·阿米森
K·迈耶
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Rhodia Operations SAS
Corteva Agriscience LLC
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Rhodia Operations SAS
Dow AgroSciences LLC
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Priority claimed from US15/152,396 external-priority patent/US10173942B2/en
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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

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  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Pyridine Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to the stable liquid preparation of the nitrification inhibitor trichloromethyl pyridine containing polar solvent, the stable liquid preparation is stablized with the compound of the trend for the polar solvent corrosion metal surface for facilitating to reduce trichloromethyl pyridine on a small quantity.Many formulations displays disclosed in the present application go out useful physics, chemical and biological activity property, including the erosion levels reduced when contacting with ferrous metal.

Description

Non-corrosive nitrification inhibitor polar solvent preparation
Related application
This application claims following equity: the United States serial 62/244,901 that on October 22nd, 2015 submits；2015 The United States serial 62/244,902 that October 22 submitted；The United States serial 62/244 submitted on October 22nd, 2015, 903, entire contents are incorporated by reference into the application.
Technical field
The present invention relates to the trichloromethyl pyridine liquid preparation of relatively non-corrosive, high loading capacity and its make and use Method, the trichloromethyl pyridine liquid preparation include polar solvent and novel metal corrosion inhibitor.
Background technique
Trichloromethyl pyridine compound, such as (inhibition such as trichloromethyl pyridine (2- chloro- 6- (trichloromethyl) pyridine) nitrification Process, and or used with the Fertilizer Combination based on nitrogen, in the fertilizer based on nitrogen such as US 3,135,594 It is described, it is incorporated by reference into the application.Applying these compounds helps to maintain to be applied to the ammonium state of soil with ammonium form Nitrogen content (the available stable state nitrogen of plant)；The plant of higher level can improve crop performance using nitrogen in soil, and can increase Add crop yield.
Due to their volatilization property, some trichloromethyl pyridine preparations (are also referred to as liquid inhibitor combination in the application Object) following application is optimal: by their mechanically coupled to soil, or about 8 after they are administered to soil surface They are poured onto soil in hour.Some trichloromethyl pyridines encapsulation preparations be suitable for trichloromethyl pyridine quick release or It dumps and is discharged into soil.It is used in particular for quick release with some trichloromethyl pyridine preparations that lignosulfonates are encapsulated to apply With being disclosed in US 4,746,513, be incorporated by reference into the application.The envelope of polycondensation disclosed in U.S.5,925,464 Dress also have been used for encapsulation agriculturally active ingredients such as trichloromethyl pyridine, especially by use polyurethane rather than polyureas encapsulate Agent improves the processing safety and storage stability of active constituent.
Compared with the liquid encapsulation preparation of trichloromethyl pyridine, the trichloromethyl pyridine preparation of encapsulation has centainly excellent Point, such as stability improve.Although encapsulation trichloromethyl pyridine preparation have the advantages that it is described, but still use trichloromethyl pyrrole The liquid encapsulation preparation of pyridine, at least partly because they tend to more easily to prepare and the tri-chlorination chloromethyl with encapsulation Pyridine preparation may be lower compared to cost.As most of any soil conditioners, the preparation agricultural containing high-content is used There are advantages for the preparation of active component.Preparation with greater activity component content generally means that and necessarily moves less material Move, store and be applied to field；Final result is that these preparations may show lower materials handling cost.
It is obtained commercially in liquid preparation most of, the content of trichloromethyl pyridine is by by trichloromethyl pyridine and relatively The limitation of corrosion-free solvent pairs.Some aspects of the invention provide the trichloromethyl comprising high relative contents trichloromethyl pyridine Pyridine liquid preparation (that is, liquid inhibitor composition).In these preparations of the invention, trichloromethyl pyridine is present in polarity In solvent, and be especially configured to previously include a large amount of polar solvents trichloromethyl pyridine preparation compared be it is free from corrosion or At least corrosivity is smaller.Dibasic ester used herein refers to containing there are two the compounds of ester group.The example of dibasic ester include but It is not limited to dimethyl glutarate, dimethyl succinate, dimethyl adipate, 2- methylglutaric acid dimethyl ester and their mixing Object.
Some embodiments include the liquid preparation of trichloromethyl pyridine, it includes: trichloromethyl pyridine, at least one pole Property solvent and at least one metal corrosion inhibitor, at least one polar solvent be selected from: (1) N, N- dialkyl group fatty acid Amide, for example, obtained in following product those, such as, but not limited to, disubstituted amide, including such as N, N- dimethyl decoyl Amine (N, N- dimethyl suet amide) and dimethyldecamide (N, N- dimethyl sheep wax amide), the change sold with following trade name Conjunction object: Hallcomid M810, Hallcomid M10, the other compounds that also can largely use, including for example ADMA 810、ADMA 10, Genagen 4166 and Genagen 4296；(2) ring Hexanone；(3) dibasic ester, such as, but not limited to 2- methylglutaric acid dimethyl ester, can obtain forIRIS, and The binary ester admixture being made of dimethyl glutarate, dimethyl succinate and dimethyl adipate, can obtain forRPDE；(4) glycol ether and polyalkylene diethylene glycol ethers, such as, but not limited to dipropylene glycol first Ether can obtain as DowanolTMDPM；(5) alkylene carbonates, such as, but not limited to propylene carbonate, can obtain for Jeffsol AG 1555；(6) 5- (dimethylamino) -2- methyl -5- oxopentanoic, can obtain for Polarclean；(7) organophosphorus compounds, such as, but not limited to trialkylphosphate, (8) alkoxy benzene compound, example Such as, but not limited to, methoxybenzene (anisole) and ethoxybenzene, (9) ketone, such as, but not limited to cyclopentanone and cyclohexanone.The present invention Liquid preparation may include the trichloromethyl pyridine of high-content, and show relatively free from corrosion property, make it is suitable for Metal object, such as metal tank and metal application apparatus.In one embodiment, alkoxy benzene compound is methoxybenzene (anisole).In one embodiment, organophosphorus compounds is triethyl phosphate.
In one embodiment, corrosion inhibitor is selected from: niacinamide, α-methylpyridine, 2,6- lutidines, epoxy Change Linseed oil (ELO) and 331 liquid epoxies of DER.
In one embodiment, corrosion inhibitor is niacin, also referred to as niacin.In another embodiment, rotten Corrosion inhibitor is nicotinic acid derivative.In another embodiment, corrosion inhibitor is niacinamide (it should be understood that term " cigarette Amide (" niacinamide) " and " niacinamide (nicotinamide) " are synonymous), iso methyl nicotinate, nicotinate, asimo Department, nicalex, niceritrol, niclonate, nicomol, hexanicotinate, oxiniacic acid or their group It closes.
The non-limiting example of nicotinic acid derivates includes that iso methyl nicotinate, nicotinate, niacinamide salicylate, niacinamide are anti- Bad hematic acid salt, niacinamide folate, niacinamide lipoate, niacinamide lactate, niacinamide glycollate, niacinamide mandelic acid Salt, niacinamide malate, niacinamide hydroxycitrate hydrochlorate, niacinamide hydroxyte-tronic acid salt, niacinamide oil ketonic acid salt, niacinamide Petroselinum hydrochlorate, niacinamide pantothenate, nicotinoyl amine gland thuja acid salt (AMP), niacinamide diphosphate (ADP), niacinamide adenosine triphosphate Hydrochlorate (ATP), niacinamide gentisate, niacin, niacinamide, acipimox (5- methylpyrazine carboxylic acid 4- oxide), nicalex, Niceritrol (bis- [[the 3- pyridine carbonyl] oxygroup] methyl of acidum nicotinicum 2,2-) -1,3- propylene glycol ester), niclonate, cigarette Sour hexamethylene alcohol ester (2,2,6,6- (1- hydroxy-cyclohexyl) tetramethyl four (Niacin Nicitinic Acid ester), hexanicotinate and oxiniacic acid (acidum nicotinicum 1- oxide).
In another embodiment, corrosion inhibitor is derivative Linseed oil comprising but it is not limited to epoxidation Asia Flaxseed oil.In another embodiment, corrosion inhibitor is 1,2- epoxyalkane, such as 1,2- decamethylene.In another kind In embodiment, corrosion inhibitor is amino alcohol, such as 2-amino-2-methyl-1-propanol (that is, AMP-95 or AMP-99).? In another embodiment, corrosion inhibitor is imidazolium compounds, such as 1- methylimidazole.In another embodiment, pole Property solvent is butyl carbitol (DGBE).In another embodiment, corrosion inhibitor and/or cosolvent are esteramides chemical combination Object.
In another embodiment, corrosion inhibitor is selected from niacinamide, iso methyl nicotinate, nicotinate, acipimox, cigarette Sour aluminium, niceritrol, niclonate, nicomol, hexanicotinate, oxiniacic acid, derivative Linseed oil (including but not limited to epoxy linseed oil), 1,2- decamethylene, amino alcohol (such as 2-amino-2-methyl-1-propanol), 1- Methylimidazole, quinolone compounds (such as quinaldine), or any combination thereof.
On the other hand, liquid fertilizer composition of the application description for agricultural application, it includes: it is one or more nitrogenous Fertiliser compounds；At least one nitrification inhibitor, it includes (trichloromethyl) pyridine compounds；Polar solvent；Optionally, rotten Corrosion inhibitor.
In one embodiment, liquid inhibitor composition or liquid fertilizer composition further include at least one another Outer component comprising but it is not limited to cosolvent, pH adjusting agent, flowable, preservative, buffer, defoaming agent, compatilizer, deposition Agent, dispersing agent, drift control agents, bleeding agent, surfactant, spreading agent and wetting agent etc..In one embodiment, nitrogenous fertilizer Compound is anhydrous ammonia.
The polar solvent that can be used for implementing some embodiments of the present invention includes but is not limited to cyclohexanone, polypropylene carbonate Ester, N, N- dialkyl group fatty acid amide: specifically, the mixture (Hallcomid of C8/C10 fatty acid N, N- diformamide M810), other fatty acid amides are also individually C8&C10N, N- diformamide, by dimethyl glutarate, dimethyl succinate With dimethyl adipate composition binary ester admixture (RPDE), (it is phosphorus to organophosphorus compounds Sour trialkyl ester) and alkoxy benzene compound (such as methoxybenzene (anisole) and ethoxybenzene).In a kind of embodiment In, organophosphorus compounds can be selected from: triethyl phosphate, tricresyl phosphate (isobutyl group) ester, tributoxyethyl phosphate (TBEP) and tri-2-ethylhexyl phosphate.In one embodiment, polar solvent includes by dimethyl glutarate, amber Dimethyl phthalate and dimethyl adipate (RPDE) and cyclohexanone composition binary ester admixture.In a kind of reality It applies in mode, alkoxy benzene compound is methoxybenzene (anisole).
The polar solvent being not acted upon in some exemplary formulations disclosed in the present application includes: (1) dipropylene glycol Monomethyl ether (Dowanol DPM), (2) 5- (dimethylamino) -2- methyl -5- oxopentanoic (Polarclean) and N- Butyl pyrrolidine ketone (TamiSolve NxG).
For implementing to be less suitable for for the present invention or even effective corrosion inhibitor includes methyl three Octyl ammonium chloride, poly- (12- hydroxyoctadecanoic acid -co- aziridine) (for example, Atlox LP6).
The corrosion inhibitor that can be used for implementing some embodiments of the present invention includes, such as pyridine carboxamide is (that is, nicotinoyl Amine (nicotinamide) or niacinamide (niacinamide)), picoline is (that is, α-methylpyridine, 2,6- dimethyl pyrazole Pyridine), epoxidation seed or vegetable oil (that is, epoxy linseed oil (ELO), epoxidised soybean oil etc.) and epoxy resin (table chlorine The liquid reacting product of pure and mild bis-phenol, such as D.E.R.TM331TMLiquid epoxies (DER 331)).
First group of embodiment includes preparation, it includes 2- chloro- 6- (trichloromethyl) pyridine, wherein chloro- 6 (three chloromethanes of 2- Base) amount of pyridine in the formulation is about 200g/L to about 400g/L；At least one polar solvent, is selected from: N, N- diformazan The mixture of base caprylamide (N, N- dimethyl suet amide) and N, N- dimethyldecamide (N, N- dimethyl sheep wax amide)； Ketone and dibasic ester, wherein polar solvent accounts for the about 40wt% to about 70wt% of the dicyandiamide solution of preparation；At least one polar solvent Miscible corrosion inhibitor, is selected from: liquid epoxies；2,6- lutidines；Epoxy linseed oil；And nicotinoyl Amine；Wherein the miscible corrosion inhibitor of the polar solvent accounts for about 0.5wt% to about 2.5wt%；With it is at least one optional Second solvent, is selected from: solvent naphtha, arsol, mineral oil, kerosene and dimethylbenzene, wherein the second solvent accounts for preparation About 5.0wt% to about 20.0wt%.
Second group of embodiment includes preparation, and it includes the 2- of about 240g/L to about 350g/L chloro- 6- (trichloromethyl) pyrroles Pyridine；The N of about 40wt% to about 60wt%, N- dimethyloctanamide (N, N- dimethyl suet amide) and N, N- dimethyldecamide The mixture of (N, N- dimethyl sheep wax amide)；The liquid epoxies and about 0.5wt% of about 0.5wt% to about 1.5wt% is extremely The 2,6- lutidines of about 1.5wt%；The solvent naphtha of about 5wt% to about 20wt%.
Third group embodiment includes preparation, and it includes the 2- of about 230g/L to about 300g/L chloro- 6- (trichloromethyl) pyrroles Pyridine；The N of about 45wt% to about 55wt%, N- dimethyloctanamide (N, N- dimethyl suet amide) and N, N- dimethyldecamide The mixture of (N, N- dimethyl sheep wax amide)；The liquid epoxies of about 0.75wt% to about 1.4wt%；About 0.5wt% is extremely The 2,6- lutidines of about 1.5wt%；The solvent naphtha of about 10wt% to about 15wt%.
4th group of embodiment includes preparation, and it includes the 2- of about 240g/L chloro- 6- (trichloromethyl) pyridines；About The N of 50.0wt% to about 55wt%, N- dimethyloctanamide (N, N- dimethyl suet amide) and N, N- dimethyldecamide (N, N- dimethyl sheep wax amide) mixture；The liquid epoxies oil of about 1.0wt% to about 1.1wt%；About 0.5wt% is to about The 2,6- lutidines of 1.5wt%；The solvent naphtha of about 11.0wt% to about 14.0wt%.
5th group of embodiment includes preparation, and it includes the 2- of about 240g/L chloro- 6- (trichloromethyl) pyridines；About The N of 50.55wt%, N- dimethyloctanamide (N, N- dimethyl suet amide) and N, N- dimethyldecamide (N, N- dimethyl Sheep wax amide) mixture；The liquid epoxies oil of about 1.2wt%；About 0.5 to about 1.5wt% 2,6- lutidines； The solvent naphtha of about 12.64wt%.
6th group of embodiment includes preparation, and it includes the 2- of about 200g/L to about 400g/L chloro- 6- (trichloromethyl) pyrroles Pyridine；The dibasic ester of about 20wt% to about 50wt%；The epoxy linseed oil of about 0.5wt% to about 2.5wt%；About 0.5wt% To the niacinamide of about 2.5wt%；The cyclohexanone of about 20.0wt% to about 50.0wt%.
7th group of embodiment includes preparation, and it includes the 2- of about 240g/L to about 350g/L chloro- 6- (trichloromethyl) pyrroles Pyridine；The dibasic ester of about 45wt% to about 55wt%；The epoxy linseed oil of about 1.0wt% to about 2.0wt%；About 0.8wt% Niacinamide；The cyclohexanone of about 11.0wt% to about 14.0wt%.
8th group of embodiment includes preparation, and it includes the 2- of about 240g/L chloro- 6- (trichloromethyl) pyridines；About The dibasic ester of 50.47wt%；The epoxy linseed oil of about 1.5wt%；The niacinamide of about 0.8wt%；About 12.62wt%'s Cyclohexanone.
9th group of embodiment includes preparation, it includes: the 2- of about 200g/L to about 400g/L chloro- 6- (trichloromethyl) pyrrole Pyridine；The dibasic ester of about 40wt% to about 60wt%；The epoxy linseed oil of about 0.5wt% to about 2.5wt%；Peace treaty The niacinamide of 0.4wt% to about 1.5wt%.
Tenth group of embodiment includes dozenth embodiment: the 2- of about 240g/L chloro- 6- (trichloromethyl) pyridine；About The dibasic ester of 63.08wt%；The epoxy linseed oil of about 1.5wt%；About 0.6 to about 1.0wt% niacinamide.
11st group of embodiment includes preparation, it includes: the 2- of about 240g/L chloro- 6- (trichloromethyl) pyridine；About The dibasic ester of 63.08wt%；The epoxy linseed oil of about 1.5wt%；The niacinamide of about 0.8wt%.
12nd group of embodiment includes preparation, it includes: the chloro- 6- of the 2- of about 200g/L to about 400g/L (trichloromethyl) Pyridine；The triethyl phosphate of about 40wt% to about 70wt%；The epoxy linseed oil of about 0.5wt% to about 2.5wt%；Peace treaty The methyl nicotinate of 0.5wt% to about 2.5wt%.
13rd group of embodiment includes preparation, it includes: the chloro- 6- of the 2- of about 200g/L to about 400g/L (trichloromethyl) Pyridine；The methoxybenzene of about 40wt% to about 70wt%；The niacinamide of about 0.5wt% to about 2.5wt%；About 0.5wt% is extremely The 2-amino-2-methyl-1-propanol of about 2.5wt%.
14th group of embodiment includes at least one system according to any group in first group to the 13rd group embodiment Agent and at least one other agricultural ingredients, at least other agricultural ingredients are selected from: herbicide, insecticide, nematicidal Agent, fungicide and fertilizer.
15th group of embodiment includes any one of the preparation of the 14th group of embodiment, wherein the agricultural ingredients It is fertilizer.
16th group of embodiment includes any one of the preparation of the 15th group of embodiment, wherein the fertilizer includes Nitrogen.
17th group of embodiment includes the method for handling soil comprising following steps: by first group to the 16th group At least one of preparation of embodiment is applied at least one region in the region being made up of: the one of soil Partial surface, the lower face of a part of soil, a part of plant, and a part on the surface adjacent with plant.
18th group of embodiment includes any one of the method for the 17th group of embodiment, and wherein step of applying includes At least one preparation is injected into a part of soil.
Specific embodiment
In order to promote the understanding to new technology principle, with reference to its preferred embodiment, and specific language will be used Speech is to describe them.It will be understood, however, that new technology involved in the new technology that those skilled in the art usually will recognize that is former It manages such changes, modifications and is further useful in the disclosure and the scope of the claims, so that anticipation does not limit new technology Range.
Unless otherwise stated, term " about " used herein refer to described value less than 10% to more than 10% It is worth range, for example, about 1.0 include 0.9 to 1.1 value.
(trichloromethyl) pyridine compounds that can be used for the present composition include having to be taken by least one trichloromethyl The compound of the pyridine ring in generation and its inorganic acid salt of these compounds.The presence of (trichloromethyl) pyridine compounds inhibits soil Or in somatomedin ammonium nitrogen nitrification, to prevent nitrogenous fertilizer, organic nitrogen component or organic fertilizer etc. from generating ammonium nitrogen Immediate loss.Suitable compound include in addition to trichloromethyl on pyridine ring the also chemical combination containing chlorine or methyl substituents Object, and including picoline, such as the chlorizate of lutidines, collidine and picoline.(trichloromethyl) pyridine The suitable salt of compound includes hydrochloride, nitrate, sulfate and phosphate.
(trichloromethyl) pyridine compounds for carrying out the present invention are typically the oily liquids or knot being dissolved in solvent Brilliant solid.Other suitable compounds are described in U.S.3,135,594.Preferably (trichloromethyl) pyridine is the chloro- 6- (three of 2- Chloromethyl) pyridine (also referred to as trichloromethyl pyridine) and product N-SERVETMThe work of (trade mark of Dow AgroSciences LLC) Property ingredient.
N-SERVETMThe loading capacity of active trichloromethyl pyridine is about 240g/L.N-SERVETMTrichloromethyl pyrrole Pyridine loading capacity part for the solubility in the solvent (for example, Aromatic100) of preparation and its is being mentioned by trichloromethyl pyridine The corrosivity of high temperature (that is, 50 DEG C) is set.It can be used in the relatively free from corrosion preparation of trichloromethyl pyridine having it again Its non-polar hydrophobic solvent includes but is not limited to other naphthalene depleted solvents, that is, includes the arsol of less than about 1% naphthalene.It can be used for The rear addition solvent for preparing some nonionic hydrophobics of trichloromethyl pyridine liquid preparation includes but is not limited to: Aromatic 100 fluids, also referred to as solvent naphtha or light aromatics；150 fluid of Aromatic, also referred to as solvent naphtha, heavy virtue Hydrocarbon, high-flash aromatic naphthas II type, heavy aromatic hydrocarbon solvent naphtha, hydrocarbon, C10 aromatic hydrocarbons, > 1% naphthalene, A150, S150；With 200 fluid of Aromatic, also referred to as solvent naphtha, heavy arene, high-flash aromatic naphthas II type, heavy Aromatic solvent naphtha, hydrocarbon, C10-13 aromatic hydrocarbons, > 1% naphthalene, A200 and S200.
Compared with nonpolar solvent, trichloromethyl pyridine tends to relatively be soluble in polar solvent.Unfortunately, trichloromethyl Preparation of the pyridine in polar solvent tends to corrosivity, especially for carbon steel storage container.At least partially due to three The corrosion property of preparation of the chloromethylpyridine in polar solvent, it has proved that they are difficult to be commercialized.Some sides of the invention Face includes identifying and using particularly useful corrosion inhibition additive, makes actual liquid system of the trichloromethyl pyridine in polar solvent Agent includes about 200 to about 400g/L trichloromethyl pyridine.Compared with being currently available that trichloromethyl pyridine polar solvent preparation, These preparations of the invention have significantly lower corrosivity.
In one embodiment, (trichloromethyl) pyridine compounds are trichloromethyl pyridines.(trichloromethyl) pyridine The 2wt% that object lower limit present in liquid inhibitor composition is composition is closed, or in other embodiments, lower limit is group The 3wt% of object is closed, or in other embodiments, lower limit is the 5wt% of composition.
In another embodiment, (trichloromethyl) pyridine compounds lower limit present in liquid inhibitor composition Be composition 0.5wt% or 1wt% or 2wt% or 3wt% or 4wt% or 5wt%, 6wt% or 8wt% or 10wt% or 12wt% or 14wt%.In another embodiment, (trichloromethyl) pyridine compounds are deposited in liquid inhibitor composition The upper limit be composition 75wt% or 65wt% or 60wt%.In another embodiment, (trichloromethyl) pyridine Close the 60wt% that object upper limit present in liquid inhibitor composition is composition.In another embodiment, (three chloromethanes Base) pyridine compounds upper limit present in liquid inhibitor composition be composition 55wt%.In another embodiment In, (trichloromethyl) pyridine compounds upper limit present in liquid inhibitor composition is the 59wt% or 57wt% of composition Or 55wt% or 53wt% or 50wt%.In another embodiment, (trichloromethyl) pyridine compounds are in liquid inhibitor The upper limit present in composition is the 48% or 46%% or 45% or 42% or 40% of composition.
The application describes the high loading capacity composition of trichloromethyl pyridine, and (in one embodiment, loading capacity is 360g/ L), stability is shown in various extreme conditions (such as cool condition).Composition described herein is also capable of providing to carbon The corrosion resistance of cylinder of steel.
In one embodiment, (trichloromethyl) pyridine compounds are dispersed in the loading capacity in liquid inhibitor composition It is at least 200g/L, or in another embodiment, at least 250g/L, or in another embodiment, at least 300g/L, Or in another embodiment, at least 320g/L, or in a kind of further embodiment, at least 340g/L, or another In a kind of embodiment, at least 360g/L, or in another embodiment, at least 380g/L, or in another embodiment In, at least 400g/L.
In one embodiment, (trichloromethyl) pyridine compounds (typically, the chloro- 6- of 2- (trichloromethyl) pyridine) exist 25 DEG C of solubility is at least 300 gram per liters (g/L), or in another embodiment, at least 320g/L, or in one kind into one In the embodiment of step, at least 340g/L, or in another embodiment, at least 360g/L, or in another embodiment In, at least 380g/L, or in another embodiment, at least 400g/L.
In one embodiment, liquid inhibitor composition is prepared as follows: making one or more nitrification inhibitors and packet Solvent contact containing at least one organophosphorus compounds, so that nitrification inhibitor is dissolved or dispersed in solvent.Liquid Inhibitor combination can further include at least one other component, typically corrosion inhibitor.
Liquid fertilizer composition described herein includes: one or more nitrogenous fertilizer compounds；At least one includes (trichlorine Methyl) pyridine compounds nitrification inhibitor；Solvent comprising organophosphorus compounds；Optionally, corrosion inhibitor.? In a kind of embodiment, liquid inhibitor composition further includes at least one other component comprising but be not limited to molten altogether Agent, pH adjusting agent, flowable, preservative, buffer, defoaming agent, compatilizer, deposition agent, dispersing agent, drift control agents, infiltration Agent, surfactant, spreading agent and wetting agent etc..
In one embodiment, nitrogenous fertilizer compound is anhydrous ammonia.
It yet still another aspect, the application describes liquid fertilizer composition, it includes the following substances of the weight based on composition: (a) relative to the weight of composition at most one or more nitrogenous fertilizer compounds of about 99wt%, in one embodiment It is anhydrous ammonia, (b) (trichloromethyl) pyridine compounds are 2- chloro- 6- (trichloromethyl) pyridine in one embodiment, (c) comprising the solvent of organophosphorus compounds, and (d) corrosion inhibitor.In one embodiment, organophosphorus ester chemical combination Object is alkylphosphonate.In one embodiment, organophosphorus compounds is triethyl phosphate.In a kind of embodiment In, organophosphorus compounds is triethyl phosphate, tricresyl phosphate (isobutyl group) ester, tributoxyethyl phosphate (TBEP) or phosphoric acid Three (2- ethylhexyl) esters.
The method of preparation liquid fertilizer composition includes making one or more nitrogenous fertilizer compounds and liquid inhibitor composition Contact, as described in the present application.In one embodiment, nitrogenous fertilizer compound is anhydrous ammonia.In one embodiment, liquid presses down Preparation compositions include at least one nitrification inhibitor, and at least one nitrification inhibitor is dissolved or dispersed in comprising at least one In the solvent of kind organophosphorus compounds.In one embodiment, nitrification inhibitor includes (trichloromethyl) pyridine chemical combination Object.In one embodiment, liquid inhibitor composition further includes at least one other component, typically corrosion suppression Preparation.
In one embodiment, liquid fertilizer composition described herein is for handling soil.A kind of embodiment In, term " processing ", which refers to, contacts composition described herein with soil.In another embodiment, term " processing " Refer to the composition and soil mechanical mixture simultaneously.In another embodiment, term " processing " refers to the combination Object is administered to soil surface, then will be in (for example, in certain depth) composition mechanically coupled to soil.In another implementation In mode, term " processing ", which refers to, is integrated to certain depth in soil for described composition, such as by injecting and irrigating.
In one embodiment, term " processing " refers to liquid fertilizer composition described herein to be less than or wait In 10 inches of depth injection soil.In another embodiment, term " processing " refers to liquid described herein Fertilizer composition is injected in soil with the depth less than or equal to 9 inches, or in some embodiments, is less than or equal to 8 English It is very little, or in some embodiments, it is less than or equal to 7 inches, or in some embodiments, less than or equal to 6 inches, or In some embodiments, it is less than or equal to 5 inches, or in some embodiments, is less than or equal to 4 inches, or in some realities It applies in mode, is less than or equal to 3 inches.
On the other hand, the application describes the method for the target plant that applies fertilizer comprising applies liquid fertilizer composition In the soil or environment of target plant, the liquid fertilizer composition includes: one or more nitrogenous fertilizer compounds；At least one packet Nitrification inhibitor containing (trichloromethyl) pyridine compounds；Solvent comprising organophosphorus compounds, and optionally, corrosion suppression Preparation.In one embodiment, liquid inhibitor composition further includes at least one other component comprising but it is unlimited In cosolvent, pH adjusting agent, flowable, preservative, buffer, defoaming agent, compatilizer, deposition agent, dispersing agent, drift control Agent, bleeding agent, surfactant, spreading agent and wetting agent etc..In one embodiment, nitrogenous fertilizer compound is anhydrous ammonia.
In one embodiment, liquid inhibitor composition described herein or liquid fertilizer composition are in following temperature Degree forms stable composition: less than or equal to 10 DEG C or 7 DEG C or 5 DEG C or 3 DEG C.In another embodiment, the application The liquid inhibitor composition of description or liquid fertilizer composition form stable composition: less than in following temperature or are equal to 0 ℃.In another embodiment, liquid inhibitor composition described herein or liquid fertilizer composition are in following temperature Form stable composition: less than or be equal to -1 DEG C or -2 DEG C or -3 DEG C or -4 DEG C or -5 DEG C or -6 DEG C or -7 DEG C or - 8 DEG C or -9 DEG C or -10 DEG C.In one embodiment, stable composition refers to is not observed wadding whithin a period of time Solidifying or crystallization.
In one embodiment, liquid inhibitor composition described herein or liquid fertilizer composition are at least 24 Stable composition is formed in hour.In one embodiment, liquid inhibitor composition or Liquid Fertilizer described herein Feed composition forms stable composition at least 48 hours.In one embodiment, liquid described herein inhibits Agent composition or liquid fertilizer composition form stable composition at least 1 week.In one embodiment, the application retouches The liquid inhibitor composition or liquid fertilizer composition stated form stable composition at least 2 weeks.
In one embodiment, composition described herein stablizes at least three moon in canister.In a kind of reality It applies in mode, (or in some embodiments, composition described herein stablizes at least 2 months at 25 DEG C in canister 50℃).In one embodiment, composition described herein stablizes at least January (or one in canister at 25 DEG C In a little embodiments, 50 DEG C).In one embodiment, canister can be carbon steel container.
It in another embodiment, is suitable for the compound of organic solvent constituent as the compositions and methods of the invention Composition stable under liquid or other situations is formed at -16 DEG C or greater than -16 DEG C of temperature with nitrification inhibitor, is being substituted In embodiment, it is greater than -14 DEG C, in other embodiments, is greater than -12 DEG C, in other embodiments, is greater than -10 DEG C, In further embodiment, it is greater than -8 DEG C, in other embodiments, is greater than -5 DEG C, in other embodiments, is greater than -3 DEG C, in other embodiments, it is greater than -2 DEG C, in other embodiments, is greater than 0 DEG C, in other embodiments, is greater than 2 DEG C, in other embodiments, it is greater than 4 DEG C, in other embodiments, is greater than 5 DEG C.
In some embodiments, in specific range of temperatures or greater than specific temperature (as described in the present application), liquid fertilizer Composition is stable, it means that nitrification inhibitor it is expected manufacture, storage and use condition not with solvent or solvent group Divide reaction.In another embodiment, in specific range of temperatures or greater than specific temperature (as described in the present application), liquid fertilizer Composition is stable, it means that liquid fertilizer composition or liquid inhibitor composition are in a phase or are substantially at In one phase, i.e., no observable crystal precipitates, and/or without observable without observable multiple liquid phases.
In one embodiment, organophosphorus compounds is the compound according to formula (I)
Wherein R1、R2And R3It is each independently selected from H, C1-C16Alkyl, C1-C16Alkenyl, C1-C16Alkoxyalkyl, C7-C30 Alkylaryl alkyl, C7-C30Aryl alkyl or aryl；Condition is R1、R2Or R3At least one of be not H.Implement in another kind In mode, R1、R2And R3It is each independently selected from H, C1-C12Alkyl, C1-C12Alkenyl, C1-C12Alkoxyalkyl, C7-C30Alkyl Aryl alkyl, C7-C30Aryl alkyl or aryl；Condition is R1、R2Or R3At least one of be not H.In one embodiment, R1、R2And R3It is each independently selected from H, C1-C4Alkyl, C4-C8Alkyl, C1-C12Alkenyl, C1-C4Alkoxyalkyl, C7-C30Alkyl Aryl alkyl, C7-C30Aryl alkyl or aryl；Condition is R1、R2Or R3At least one of be not H.
In yet another embodiment, R1、R2And R3It is each independently selected from linear chain or branched chain C1-C12Alkyl, linear chain or branched chain C1-C12Alkenyl, linear chain or branched chain C1-C12Alkoxyalkyl, linear chain or branched chain C7-C30Alkylaryl alkyl, linear chain or branched chain C7- C30Aryl alkyl or aryl.In one embodiment, R1、R2And R3It is each independently selected from C1-C12Alkyl is more typically C2-C8Alkyl.
In one embodiment, R1、R2And R3It is C each independently1-C3Alkyl, typically ethyl.Another real It applies in mode, R1、R2And R3It is branch C each independently1-C12Alkyl, typically 2- ethylhexyl.In a kind of embodiment In, R1、R2And R3It is C each independently1-C12Alkoxyalkyl, typically butoxyethyl group.
By described in detail below and embodiment, the present invention described herein be will be apparent, and be wrapped in one aspect The liquid inhibitor composition and/or liquid fertilizer composition for agricultural application are included, the liquid fertilizer composition includes: extremely A kind of few nitrification inhibitor comprising (trichloromethyl) pyridine compounds；Polar solvent comprising at least two following polar solvents Blend: (i) binary ester blend and (ii) ketone such as cyclohexanone；Optionally, corrosion inhibitor.
On the other hand, the method that the application description prepares liquid inhibitor combination comprising by one or more nitrifications Inhibitor is contacted with the polar solvent blend comprising at least two following polar solvents: (i) binary ester blend and (ii) ketone Such as cyclohexanone, so that nitrification inhibitor is dissolved or dispersed in polar solvent mixture.In one embodiment, it nitrifies Inhibitor includes (trichloromethyl) pyridine compounds.In one embodiment, liquid inhibitor composition further include to A kind of few other component, typically corrosion inhibitor.
On the other hand, liquid fertilizer composition of the application description for agricultural application, the liquid fertilizer composition packet It includes: one or more nitrogenous fertilizer compounds；At least one includes the nitrification inhibitor of (trichloromethyl) pyridine compounds；Comprising at least The polar solvent blend of two kinds of following polar solvents: (i) binary ester blend and (ii) ketone such as cyclohexanone；Optionally, Corrosion inhibitor.
In some embodiments, binary ester blend includes:
The diester of formula (IIa):
The diester of formula (IIb):
The diester of formula (IIc):
R1And/or R2The hydrocarbon with about 1 to about 8 carbon atom can be individually comprised, typically, methyl, ethyl, propyl, Isopropyl, butyl, isobutyl group, normal-butyl, isopentyl, hexyl, heptyl or octyl.
In certain other embodiments, binary ester blend includes:
The diester of formula (IIIa):
The diester of formula (IIIb):
The diester of formula (IIIc):
R1And/or R2The hydrocarbon with about 1 to about 8 carbon atom can be individually comprised, typically, methyl, ethyl, propyl, Isopropyl, butyl, isobutyl group, normal-butyl, isopentyl, hexyl, heptyl or octyl.In such an embodiment, blend is logical The often diester of the formula (IIIa) comprising (weight relative to blend) (i) about 5% to about 30%, (ii) about 70% to about 95% Formula (IIIb) diester, and (iii) about 0% to about 10% formula (IIIc) diester.More typically, blend generally comprises (weight relative to blend): the diester of the formula (IIIa) of (i) about 6% to about 12%, the formula of (ii) about 86% to about 92% (IIIb) diester, and (iii) about 0.5% to about 4% formula (IIIc) diester.
Most typically, blend includes (weight relative to blend): the diester of the formula (IIIa) of (i) about 9%, (ii) The diester of about 89% formula (IIIb), and (iii) about 1% formula (IIIc) diester.Blend is generally characterized by: flash-point is 98 DEG C, it is less than about 10Pa in 20 DEG C of vapour pressures and vapo(u)rizing temperature is about 200 DEG C -275 DEG C.
In some embodiments, polar solvent blend include (weight relative to solvent blend) at most The ketone of 100wt% or 99.9wt%.In one embodiment, polar solvent blend includes (to be blended relative to polar solvent The total weight of object) the at most ketone of 80wt%.In one embodiment, polar solvent blend includes (relative to polar solvent The total weight of blend) the at most ketone of 90wt%.In one embodiment, polar solvent blend includes (relative to polarity The total weight of solvent blend) the at most ketone of 70wt%.In one embodiment, polar solvent blend include (relative to The total weight of polar solvent blend) the at most ketone of 65wt%.In one embodiment, polar solvent blend includes (phase For the total weight of polar solvent blend) the at most ketone of 60wt%.In one embodiment, polar solvent blend includes (total weight relative to polar solvent blend) at most ketone of 55wt%.In one embodiment, polar solvent blend Include (total weight relative to polar solvent blend) the at most ketone of 50wt%.In one embodiment, polar solvent is total Mixed object includes (total weight relative to polar solvent blend) at most ketone of 45wt%.In one embodiment, polarity is molten Agent blend includes (total weight relative to polar solvent blend) at most ketone of 40wt%.Think polar solvent blend Composition allows loading capacity described herein.
The Sutable examples of ketone include but is not limited to below any one or more of: acetone, methyl ethyl ketone, methyl propyl ketone, It is cyano propanone, ethyoxyl acetone, acetonyl acetone, diacetone alcohol, methyl iso-butyl ketone (MIBK), metacetone, diisopropyl ketone, two different Butyl ketone, methyl-n-amyl ketone, methyl n hexyl ketone, cyclopentanone, methyl cyclohexanone, cyclohexanone, methallyl pentylcyclohexanone, benzene Pentylcyclohexanone, cyclohexyl ring hexanone, benzyl cyclohexanone, phorone, isophorone and B- irisone, methyl vinyl ketone, first Base isopropenyl ketone, methylpropenyl ketone, Mesityl oxide, chlroacetone, acetophenone, benzophenone, methyl 2- naphthyl ketone, benzene Acetone, n-butyrophenone, to acetyl biphenyl, melilotal, acetanisole, parachloroacetophenone, acetoacetate Ethyl ester, acetoacetate nitrile, acetoacetate amide, acetyl group p-cymene, dibenzyl ketone etc..In one embodiment, ketone is Cyclohexanone.
In some embodiments, binary ester blend includes the adduct of pure and mild straight chain diacid, and each adduct has formula (IV):
R-OOC-A-COO-R
(IV)
Wherein R is alkyl (for example, methyl, ethyl etc.), and A is-(CH2)4-、-(CH2)3With-(CH2)2Mixture.? In other embodiment, blend includes the adduct of alcohol (typically, ethyl alcohol) and straight chain diacid, and the adduct has formula R1-OOC-A-COO-R2, wherein R1And/or R2At least part be at least one straight chain alcohol with 4 carbon atoms and/or The residue of at least one linear chain or branched chain alcohol at least five carbon atom, and wherein A is divalent straight hydrocarbon.In some realities It applies in mode, A is-(CH2)4-、-(CH2)3With-(CH2)2One of or mixture.In other embodiments, dibasic ester Adduct including pure and mild linear chain or branched chain diacid, the adduct have formula (IV): R-OOC-A-COO-R, wherein R is alkyl (for example, methyl, ethyl etc.), A is one of following :-(CH2)4-、-(CH2)3、-(CH2)2-、-CH2Or its any mixing Object.
Binary ester blend can be originated from polyamide such as polyamide 6, one of 6 preparations or a variety of by-products.One In kind embodiment, at least one dibasic ester includes adipic acid, the linear chain or branched chain of glutaric acid and succinic acid, ring-type or non-annularity C1-C20Alkyl, aryl, alkylaryl or alkyl aryl blend.In another embodiment, composition include oneself two Linear chain or branched chain, ring-type or the non-annularity C of acid, methylglutaric acid and ethylsuccinic acid diacid1-C20Alkyl, aryl, alkylaryl Or the blend of alkyl aryl.
In general, polyamide is the copolymer of the condensation reaction to be formed by reacting diamines and dicarboxylic acids preparation.Specifically, Polyamide 6,6 be the condensation formed by diamines (typically, hexamethylene diamine) and dicarboxylic acids (typically, adipic acid) reaction React the copolymer of preparation.
In one embodiment, the blend of dibasic ester, which can be originated from, is used to prepare the adipic acid reaction of polyamide, closes At and/or preparation one of or a variety of by-products, the composition include adipic acid, glutaric acid and amber acid diacid dioxane The blend of base ester copolymer (the application is sometimes referred to as " AGS " or " AGS blend ").In one embodiment, dibasic ester Blend includes dimethyl adipate, dimethyl glutarate and dimethyl succinate.
In one embodiment, the blend of ester is originated from for six in polyamide (typically, polyamide 6,6) preparation By-product in methylene diamine reaction, synthesis and/or preparation.The composition includes methylglutaric acid, ethylsuccinic acid two (the application is sometimes referred to as " MGA ", " MGN ", " MGN blend " or " MGA to the blend of the dialkyl ester of sour and optional adipic acid Blend ").In one embodiment, binary ester blend includes dimethyl adipate, methylglutaric acid dimethyl ester and ethyl Dimethyl succinate.
In one embodiment, liquid inhibitor composition or liquid fertilizer composition further include at least one another Outer component comprising but it is not limited to cosolvent, pH adjusting agent, flowable, preservative, buffer, defoaming agent, compatilizer, deposition Agent, dispersing agent, drift control agents, bleeding agent, surfactant, spreading agent and wetting agent etc..In one embodiment, nitrogenous fertilizer Compound is anhydrous ammonia.
On the other hand, the method that the application describes preparation liquid fertilizer composition, it is one or more the method includes making Nitrogenous fertilizer compound is contacted with liquid inhibitor composition.In one embodiment, nitrogenous fertilizer compound is anhydrous ammonia.In a kind of reality Apply in mode, liquid inhibitor composition includes at least one nitrification inhibitor, at least one nitrification inhibitor dissolution or It is dispersed in solvent mixture, the solvent mixture includes at least two following solvents: (i) binary ester blend and (ii) ketone Such as cyclohexanone.In one embodiment, nitrification inhibitor includes (trichloromethyl) pyridine compounds.In a kind of embodiment In, liquid inhibitor composition further includes at least one other component, typically corrosion inhibitor.
In another embodiment, one or more second solvents can be used for that (trichlorine is dissolved or dispersed with high loading capacity Methyl) pyridine compounds, second solvent includes but is not limited to solvent naphtha, arsol, mineral oil, kerosene and chlorine Change aliphatic series and aromatic hydrocarbon.In a kind of specific embodiment, for (trichloromethyl) pyridine to be dissolved or dispersed with high loading capacity One or more second solvents of compound include but is not limited to dimethylbenzene and solvent naphtha.
In a kind of specific embodiment, cosolvent is the esteramides compound according to formula (II):
R1OOC-A-CONR2R3(II)
Wherein:
A is divalent straight or branch (C2-C8) aliphatic group, R1, R2 and R3 are (C each independently1-C12) alkyl, (C1- C12) aryl, (C1-C12) alkylaryl or (C1-C12) aryl alkyl, R2 and R3 can respectively be optionally substituted with one or more hydroxyls Base.
It is choosing that (trichloromethyl) pyridine compounds preparation of the invention, which can be applied to soil or the rate of application of somatomedin, It is limited under at least one of freedom about 0.1, about 0.25, about 0.5 and the group of about 0.58kg/ hectares of lower limit composition selected from by about 1.0, about 1.2 and about 1.5kg/ hectares the upper limit composition group at least one upper limit.In view of such as soil pH, temperature, soil The factors such as earth type and administration mode, preferred amounts can be determined easily by the preferred option applied.
Preparation of the invention can by be beneficial to purpose crop it is any in a manner of apply.In one embodiment, it incite somebody to action this The preparation of invention is applied to somatomedin in such a way that row replacement or ridge are applied.In another embodiment, it is being inoculated with or is transplanting institute Before needing crops, preparation is applied to growth medium or is applied to entire growth medium.In another embodiment, Preparation can be applied to the root zone of growing plant.
It can be to prepare soil with the mutually compatible any convenient manner of use of the invention comprising by preparation and soil machine Tool mixing.Other applications can also include that preparation is administered to soil surface, then draw, cut or preparation is cut to soil In reach required depth.It further includes injection, sprinkling or irrigation etc. that nitrification inhibitor, which is transported to other methods in soil, Method.In numerous applications, trichloromethyl pyridine compound is transported to and reaches up to 6 inches (15.24 centimetres) in soil Required depth.
In some embodiments, trichloromethyl pyridine preparation of the invention can for example be killed with other agriculturally active ingredients Insect agent, fungicide, nematicide, herbicide etc. are used together.
The some exemplary herbicides that can be used together with trichloromethyl pyridine preparation of the invention include but is not limited to second Careless amine (acetochlor), alachlor (alachlor), chlorine Fampridine is sour (aminopyralid), atrazine (atrazine), Benoxacor (benoxacor), Brominal (bromoxynil), fluorine ketazolam grass (carfentrazone), green sulphur are grand (chlorsulfuron), clodinafop-propargyl (clodinafop), clopyralid (clopyralid), dicamba (dicamba), standing grain Careless spirit (diclofop-methyl), dimethenamid (dimethenamid), fenoxaprop-P (fenoxaprop), fluorine ketone sulphur Grand (flucarbazone), flufenacet (flufenacet), Flumetsulam (flumetsulam), flumiclorac (flumiclorac), fluroxypyr (fluroxypyr), glufosinate-ammonium (glufosinate-ammonium), glyphosate (glyphosate), halosulfuronmethyl (halosulfuron-methyl), miaow oxalic acid (imazamethabenz), imazamox (imazamox), Arsenal (imazapyr), Scepter (imazaquin), Imazethapyr (imazethapyr), different evil fluorine humulone (isoxaflutole), dichloro quinolinic acid (quinclorac), 2 first, 4 chlorine (MCPA), MCP amine (MCP amine), 2 first, 4 chlorine is different Monooctyl ester (MCP ester), Metalaxyl-M (mefenoxam), mesotrione (mesotrione), isopropyl methoxalamine (metolachlor), S- isopropyl methoxalamine (s-metolachlor), metribuzin (metribuzin), metsulfuron-methyl (metsulfuron methyl), nicosulfuron (nicosulfuron), paraquat (paraquat), Pendimethalin (pendimethalin), picloram (picloram), primisulfuronmethyl (primisulfuron), procarbazone (propoxycarbazone), the third sulphur of fluorine is grand (prosulfuron), pyraflufen ethyl, rimsulfuron 25 (rimsulfuron), Simanex (simazine), Sulfosulfuron (sulfosulfuron), thifensulfuronmethyl (thifensulfuron), benzene pyrazoles humulone (topramezone), methoxyphenone (tralkoxydim), tri-allate (triallate), triasulfuron (triasulfuron), tribenuron-methyl (tribenuron), Triclopyr (triclopyr), fluorine are happy Clever (trifluralin), 2,4- drops (2,4-D), 2,4- drop amine (2,4-D amine), 2,4- drop esters (2,4-D ester) etc., Tomatotone (4-CPA), chlorobenzene oxy butyrate (4-CPB), chlorine phenoxy propionic acid (4-CPP), 2,4- drops (2,4-D), 3,4-DA, 2,4- drops Butyric acid (2,4-DB), 3,4- Embutoxs (3,4-DB), Menaphtame (2,4-DEB), 2,4- drop phosphides (2,4-DEP), 3,4- drop propionic acid (3,4-DP), 2,4,5- tears butyric acid (2,4,5-TB), careless bud fear (2,3,6-TBA), allidochlor (allidochlor), mowing amine (acetochlor), acifluorfen (acifluorfen), aclonifen (aclonifen), alachlor (alachlor), dogstail Go out (alloxydim), pentachloro- oxopentanoic acid (alorac), special saliva ketone (ametridione), ametryn (ametryn), special grass piperazine ketone (amibuzin), amicarbazone (amicarbazone), sulphur ammonia sulphur is grand (amidosulfuron), cyclopropyl pyrimidine acid (aminocyclopyrachlor), chloroaminopyridine is sour (aminopyralid), chloroaminopyridine acid (aminopyralid), It is grand to dredge grass for amiprophos-methyl (amiprofos-methyl), Amrol (amitrole), anilofos (anilofos) (anisuron), sulphur grass is clever (asulam), and sulphur grass is clever (asulam), atraton (atraton), atrazine (atrazine), azoles Pyridine alkynes is careless (azafenidin), and tetrazolium sulphur is grand (azimsulfuron), and nitrine is net (aziprotryne), oatax (barban), BCPC, beflubutamid (beflubutamid), benazolin (benazolin), bencarbazone, benfluralin (benfluralin), benfuresate (benfuresate), bensulfuron-methyl (bensulfuron), bensulide (bensulide) go out Careless pine (bentazone), benzadox (benzadox), benzfendizone (benzfendizone), benzyl grass amine (benzipram), The bicyclic ketone of benzo (benzobicyclon), benzofenap (benzofenap), fluorine sulfanilamide (SN) is careless (benzofluor), suffer (benzoylprop), benzthiazuron (benzthiazuron), bicylopyrone, bifenox (bifenox), bilanafos (bilanafos), bilanafos (bilanafos), double phonetic benzoic acid (bispyribac), bromacil (bromacil), chaff Oxalic acid dinitrile (bromobonil), bromobutide (bromobutide), Faneron (bromofenoxim), Brominal (bromoxynil), it is quick (brompyrazon) to kill green bristlegrass, butachlor (butachlor), butafenacil (butafenacil), suppression Careless phosphine (butamifos), butenachlor (butenachlor), special imidazoles is careless (buthidazole), tebuthiuron (buthiuron), Amex820 (butralin), butroxydim (butroxydim), buturon (buturon), butylate (butylate), benzophenone azoles (cafenstrole), benzophenone azoles (cafenstrole), kecaoan ester (cambendichlor), card Bar grass is clever (carbasulam), and kappa grass is clever (carbasulam), carbetamide (carbetamide), special oxazole prestige (carboxazole), grass loses dead (chlorprocarb), fluorine ketazolam grass (carfentrazone), and grass is vertical dead (CDEA), double chlorine Clever (CEPC), chlomethoxynil (chlomethoxyfen), Amiben (chloramben), chloranocryl (chloranocryl), alkynes Standing grain spirit (chlorazifop), chlorazine (chlorazine), bromax (chlorbromuron), chlorbufam (chlorbufam), ethoxy benzene is grand (chloreturon), Fenac (chlorfenac), Bidisin (chlorfenprop), fluorine It is phonetic to kill (chlorflurazole), chloroflurenol (chlorflurenol), chloridazon (chloridazon), chlorimuronethyl (chlorimuron), Mo 9 granular (chlornitrofen), chloropon (chloropon), chlorine wheat are grand (chlorotoluron), chloroxifenidium (chloroxuron), chloroxynil (chloroxynil), chlorpropham (chlorpropham), green sulphur is grand (chlorsulfuron), chlorine phthalandione (chlorthal), chlorothiamid (chlorthiamid), Cinidon-ethyl (cinidon-ethyl), cinmethylin (cinmethylin), cinosulfuron (cinosulfuron), cisanilide (cisanilide), clethodim (clethodim), iodine chlorine pyridine ester (cliodinate), clodinafop-propargyl (clodinafop), neoprene grass (clofop), clomazone (clomazone), clomeprop (clomeprop), clomeprop (clomeprop) adjust tartaric acid (cloprop), cyclobutane humulone (cloproxydim), clopyralid (clopyralid), clopyralid (clopyralid), cloransulammethyl (cloransulam), chloramines are pitched careless (CPMF), and chlorine third is clever (CPPC), credazine (credazine), cumyluron (cumyluron), cyanatryn (cyanatryn), cyanazine (cyanazine), cycloate (cycloate), cyclopropyl sulphur is grand (cyclosulfamuron), cycloxydim (cycloxydim), Alipur-O (cycluron), cyanogen fluorine Careless ester (cyhalofop), herbage is fast (cyperquat), cyprazine (cyprazine), three ring taps grass amine (cyprazole), ring Acyl grass amine (cypromid), vanilla is grand (daimuron), Dalapon (dalapon), dazomet (dazomet), and it is happy to oppose grass (delachlor), desmedipham (desmedipham), desmetryn (desmetryn), Avadex (diallate), dicamba (dicamba), dichlobenil (dichlobenil), dichloral urea (dichloralurea), dichlormate (dichlormate), 2,4- It drips propionic acid (dichlorprop), essence 2,4- drop propionic acid (dichlorprop-P), chloroformate grass (diclofop), the phonetic sulfanilamide (SN) of azoles (diclosulam), diethyl weeding is bis- (diethamquat), pacifies tower (diethatyl), fluorobenzene penetenoic acid (difenopenten), difenoxuron (difenoxuron), benzene oppose fast (difenzoquat), diflufenican (diflufenican), difluoro pyrrole is grand (diflufenzopyr), dimefuron (dimefuron), dimepiperate (dimepiperate), kecaoan (dimethachlor), penta Kusatsu (dimethametryn), dimethenamid (dimethenamid), smart dimethenamid (dimethenamid-P), enemy are gone out raw (dimexano), and meter Da Song is opposed (dimidazon), dinitramine (dinitramine), dinitramine (dinitramine), Di Lete (dinofenate), the third nitre phenol (dinoprop), dinosam (dinosam), dinoseb (dinoseb), dinoterb (dinoterb), enide (diphenamid), sancap (dipropetryn), diquat dibromide (diquat), 2,4- drop sulfuric acid (disul), dithiopyr (dithiopyr), diuron (diuron), dow crabgrass killer (DMPA), Chemox PE (DNOC), EBEP, Radix Glycyrrhizae saliva (eglinazine), Endothall (endothal), sulphur azoles is careless (epronaz), and sulphur azoles is careless (epronaz), herbicide (EPTC), erbon (erbon), Esprocarb (esprocarb), fourth fluchloralin (ethalfluralin), ethametsulfuron (ethametsulfuron), thiadiazoles is grand (ethidimuron), ethiolate (ethiolate), ethofumesate (ethofumesate), ethoxyfenethyl (ethoxyfen), second Oxygen Sulfometuron Methyl (ethoxysulfuron), etinofen (etinofen), ethamine grass ether (etnipromid), ethamine grass ether (etnipromid), ethamine grass ether (etnipromid), ethoxy benzoyl is careless (etobenzanid), bexide (EXD), acyl benzene sulphur Prestige (fenasulam), acyl benzene sulphur prestige (fenasulam), acyl benzene sulphur prestige (fenasulam), 2,4,5- tears propionic acid (fenoprop), Fenoxaprop-P (fenoxaprop), fenoxapropPethyl (fenoxaprop-P), fenoxasulfone, chlorophenoxyethanol (fenteracol), diclofop-methyl thiazole (fenthiaprop), fentrazamide (fentrazamide), fenuron (fenuron), Strong fluorine (flamprop-M), flazasulfuron (flazasulfuron), florasulam (florasulam), pyrrole fluorine dogstail Clever (fluazifop), efficient fluazifop (fluazifop-P), fluazolate (fluazolate), flucarbazonesodium (flucarbazone), flucetosulfuron (flucetosulfuron), fluchloralin (fluchloralin), flufenacet (flufenacet), fluorobenzene pyrrole is careless (flufenican), flufenpyrethyl (flufenpyr), fluorine ethofumesate (flumetsulam), trifluoro oxazines (flumezin), Flumiclorac pentyl (flumiclorac), flumioxazin (flumioxazin), alkynes grass amine (flumipropyn), fluometuron (fluometuron), fluorodifen (fluorodifen), second Fluoroglycofen (fluoroglycofen), ethofumesate (fluoromidine), fluoronitrofen (fluoronitrofen), fluorobenzene is grand (fluothiuron), flupoxam (flupoxam), flupoxam (flupoxam), flupropacil, tetrafluoro propionic acid (flupropanate), fluorine pyridine sulphur is grand (flupyrsulfuron), fluridone (fluridone), fluorochloridone (flurochloridone), fluroxypyr (fluroxypyr), flurtamone (flurtamone), up to careless fluorine (fluthiacet), fomesafen (fomesafen), fomesafen (fomesafen), foramsulfuron (foramsulfuron), phosphine ammonium is plain (fosamine), fluorine furan grass ether (furyloxyfen), glufosinate (glufosinate), grass Sweet phosphine (glyphosate), fluorine chloropyridine ester (halauxifen), fluorine nitre sulfonamide (halosafen), fluorine nitre sulfonamide (halosafen), pyrrole chlorsulfuron (halosulfuron), halogen grass is fixed (haloxydine), haloxyfop (haloxyfop), Smart fluazifop-butyl (haloxyfop-P), Hexazinone (hexazinone), miaow grass ester (imazamethabenz), imazamox (imazamox), AC 263222 (imazapic), Arsenal (imazapyr), Scepter (imazaquin), Imazethapyr (imazethapyr), pyridine miaow sulphur is grand (imazosulfuron), indanofan (indanofan), indaziflam, iodine oxalic acid dinitrile (iodobonil), iodine sulphur is grand (iodosulfuron), ioxynil (ioxynil), ipazine (ipazine), Ipfencarbazone, Bing Caoding (iprymidam), Burimamide (isocarbamid), isoprocil (isocil), isomethiozin (isomethiozin), isonoruron (isonoruron), nitrogenCareless (isopolinate), isopropalin (isopropalin), isoproturon (isoproturon), isouron (isouron), ixoxaben (isoxaben), different evil chlorine Humulone (isoxachlortole), different evil fluorine humulone (isoxaflutole) dislike careless ether (isoxapyrifop), karbutilate (karbutilate), ketospiradox, lactofen (lactofen), lenacil (lenacil), linuron (linuron), 2 first, 4 chlorine (MCPA), phenothiol (MCPA-thioethyl), Thistrol (MCPB), Vi par (mecoprop), mecopropP (mecoprop-P), fourth nitre phenol (medinoterb), mefenacet (mefenacet), Mefluidide (mefluidide), green bristlegrass of going out saliva (mesoprazine), mesosulfuron (mesosulfuron), methyl sulphur grass Ketone (mesotrione), metham-sodium (metam), metamifop (metamifop), metamifop (metamifop), benzene piperazine Humulone (metamitron), metazachlor (metazachlor), bis ether halosulfuronmethyl (metazosulfuron), fluorine are rattled away grass (metflurazon), methabenz thiazuron (methabenzthiazuron), fluorine alkene nitre is careless (methalpropalin), methazole (methazole), first sulphur benzene prestige (methiobencarb), methiozolin, methiuron (methiuron), methiuron (methiuron), methometon (methometon), metoprotryn (methoprotryne), phenylpropyl alcohol is grand (methyldymron), color Man Long (metobenzuron), metobromuron (metobromuron), isopropyl methoxalamine (metolachlor), S- isopropyl methoxalamine (S-metolachlor), azoles grass sulfanilamide (SN) (metosulam), metoxuron (metoxuron), metribuzin (metribuzin), methylsulphur Grand (metsulfuron), Hydram (molinate), monalide (monalide), special dimefuron (monisouron), monochloro For acetic acid (monochloroacetic acid), afesin (monolinuron), telvar (monuron), Ceroxone (morfamquat), naproanilide (naproanilide), napropamide (napropamide), quinclorac (naptalam), neburea (neburon), nicosulfuron (nicosulfuron), pyrrole chlorine grass amine (nipyraclofen), nitralin (nitralin) remove Careless ether (nitrofen), fluoroform grass ether (nitrofluorfen), monometflurazone (norflurazon), herban (noruron), Goodrich oktone (OCH), orbencarb (orbencarb), orthosulfamuron, oryzalin (oryzalin), oryzalin (oryzalin), the third oxazole of alkynes is careless (oxadiargyl), Lonster (oxadiazon), dislikes pyrazon (oxapyrazon), cyclopropyl Oxygen sulphur is grand (oxasulfuron), and chlorine oxazines is careless (oxaziclomefone), Oxyfluorfen (oxyfluorfen), grand to lying prostrate (parafluron), paraquat (paraquat), pebulate (pebulate), n-nonanoic acid (pelargonic acid), pendimethalin (pendimethalin), penoxsuam (penoxsulam), pentanochlor (pentanochlor), penta oxazole grass (pentoxazone), perfluidone (perfluidone), pethoxamid (pethoxamid), phenisopham (phenisopham), sweet tea Dish is peaceful (phenmedipham), phenmedipham-ethyl (phenmedipham-ethyl), phenobenzuron (phenobenzuron), ammonia chlorine Pyridine acid (picloram), picloram (picloram), fluorine metazachlor (picolinafen), fluorine metazachlor (picolinafen), pinoxaden (pinoxaden), piperophos (piperophos), wheatgrass amine (pretilachlor), fluorine Sulfometuron Methyl (primisulfuron), ring cyanogen saliva (procyazine), prodiamine (prodiamine), prodiamine (prodiamine), profluazol (profluazol), profluralin (profluralin), clefoxidim (profoxydim), Third grass stops saliva (proglinazine), prometon (prometon), prometryn (prometryn), propachlor (propachlor), Propanil (propanil), propaquizafop (propaquizafop), propazine (propazine), Chem hoe (propham), isopropyl grass Amine (propisochlor), procarbazone (propoxycarbazone), piperazine imidazoles Sulfometuron Methyl (propyrisulfuron), alkynes Benzoyl grass amine (propyzamide), sulphur imines is careless (prosulfalin), prosulfocarb (prosulfocarb), and the third sulphur of fluorine is grand (prosulfuron), Good-rite n.i.x. (proxan), prynachlor (prynachlor), than reaching agriculture (pydanon), pyraclonil (pyraclonil), fluorine carfentrazone (pyraflufen), pyrasulfotole, pyrazolate (pyrazolynate), pyrazosulfuron (pyrazosulfuron), pyrazoxyfen (pyrazoxyfen), phonetic benzene grass oxime (pyribenzoxim), pyributicarb (pyributicarb), daxtron (pyriclor), pyridafol, pyridate (pyridate), pyriftalid (pyriftalid), oxime pyridine is careless (pyriminobac), pyrimisulfan, pyrithiobacsodium (pyrithiobac), Pyroxasulfone, pyroxsulam (pyroxsulam), dichloro quinolinic acid (quinclorac), quinmerac (quinmerac), quinoclamine (quinoclamine), chlorine algae amine (quinonamid), quizalofop-ethyl (quizalofop), smart quinoline standing grain Clever (quizalofop-P), sulphur benzonitrile ethamine (rhodethanil), rimsulfuron 25 (rimsulfuron), another fourth saliva (sebuthylazine), secbumeton (secbumeton), sethoxydim (sethoxydim), Tupersan (siduron), Simanex (simazine), Gesadrual (simeton), symetryne (simetryn), sulphur humulone (sulcotrione), sulfallate (sulfallate), sulfentrazone (sulfentrazone), Sulfometuron Methyl (sulfometuron), second sulphur sulphur are grand (sulfosulfuron), a word used for translation sulphur in heptan ester (sulglycapin), swep (swep), tebutam (tebutam), Metribuzin (tebuthiuron), tefuryltrione, tembotrione, tepraloxydim (tepraloxydim), terbacil (terbacil), terbucarb (terbucarb), violent herbicide (terbuchlor), terbumeton (terbumeton), Garagard (terbuthylazine), terbutryn (terbutryn), fluorine oxygen is grand (tetrafluron), thiophene ether grass amine (thenylchlor), It is grand (thiazafluron) to match azoles, thiazopyr (thiazopyr) and trichlopyr (triclopyr), thiadiazoles amine (thidiazimin), match diazole is plain (thidiazuron), and match diazole is plain (thidiazuron), and thiophene ketone sulphur is grand-methyl (thiencarbazone-methyl), thifensulfuron methyl (thifensulfuron), benthiocarb (thiobencarb), fourth grass prestige (tiocarbazil), phonetic careless amine (tioclorim), topramezone, methoxyphenone (tralkoxydim), tri-allate (tri- Allate), triasulfuron (triasulfuron), triaziflam (triaziflam), tribenuron-methyl (tribenuron), herbicide Fear (tricamba), tridiphane (tridiphane), trietazine (trietazine), trifloxysulfuron (trifloxysulfuron), trefanocide (trifluralin), triflusulfuronmethyl (triflusulfuron), trifluoromethoxy phenoxy propionic acid (trifop), trifluoro dogstail oxime (trifopsime), cyanuric acid (trihydroxytriazine), trimeturon (trimeturon), indanofan (tripropindan), tritac (tritac), tritosulfuron (tritosulfuron) go out Careless violent (vernolate), the compound of xylachlor (xylachlor) and following formula
Wherein Ar indicates to replace the phenyl for having one to four substituent group, and the substituent group is independently selected from halogen, C1-C6 Alkyl, C1-C6Alkoxy, C2-C4Alkoxyalkyl, C2-C6Alkyl-carbonyl, C1-C6Alkylthio group, C1-C6Halogenated alkyl, C1-C6Halogen For alkoxy, C2-C4Halogenated alkoxy alkyl, C2-C6Halogenated alkyl carbonyl, C1-C6Halogenated alkylthio ,-OCH2CH2-、- OCH2CH2CH2-、-OCH2O- or-OCH2CH2O-；R indicates H or F；X indicates Cl or vinyl；Cl, vinyl or first are indicated with Y Oxygroup；And their salt and ester, such as such as US7314849B2, US7300907B2, US7786044B2 and US7642220B2 Disclosed in.Depending in the presence of the component of invention formulation use herbicidal compounds stability and compound it is excellent Administration mode is selected, these compounds can be applied together with trichloromethyl pyridine preparation of the invention.It in many cases, can be with Compound is applied by any suitable mode before or after preparation of the invention is applied to soil.
The particularly suitable herbicide that can be used for composition described herein and method includes 2,4- drops (2,4-D), and 2, 4- Embutox (2,4-DB), cyclopropyl pyrimidine acid (aminocyclopyrachlor), chloroaminopyridine acid (aminopyralid), Clopyralid (clopyralid), dicamba (dicamba), fluroxypyr (fluroxypyr), fluorine chloropyridine ester (halauxifen), 2 first, 4 chlorine (MCPA), Thistrol (MCPB), picloram (picloram), trichlopyr (triclopyr), Acetochlor (acetochlor), atrazine (atrazine), benfluralin (benfluralin), chlorine ester sulphur grass Amine (cloransulam), cyhalofop-butyl (cyhalofop), the phonetic sulfanilamide (SN) of azoles (diclosulam), dithiopyr (dithiopyr), Fourth fluchloralin (ethalfluralin), florasulam (florasulam), fluorine ethofumesate (flumetsulam), glufosinate (glufosinate), glyphosate (glyphosate), haloxyfop (haloxyfop), ixoxaben (isoxaben), Monosodium methanearsonate (MSMA), oryzalin (oryzalin), Oxyfluorfen (oxyfluorfen), pendimethalin (pendimethalin), penoxsuam (penoxsulam), propanil (propanil), pyroxsulam (pyroxsulam), Quizalofop-ethyl (quizalofop), Metribuzin (tebuthiuron), the compound of trefanocide (trifluralin) and following formula.
And its C1-C12Alkyl or C7-C12Alkyl aryl or salt derivative, such as benzyl ester.
The some exemplary insecticides that can be used together with trichloromethyl pyridine preparation of the invention include but is not limited to, Avermectin (abamectin), accephate (acephate), acetamiprid (acetamiprid), fluoranthene (acrinathrin), α-cypermethrin (alpha-cypermethrin), α -5a,6,9,9a-hexahydro-6,9-methano-2,4 (alpha-endosulfan), Ai Zhading (azadirachtin), azinphos ethyl (azinphos-ethyl), azinphos-methyl (azinphos-methyl), azoles worm prestige (bendiocarb), rosickyite Ke Baiwei (benfuracarb), bensultap (bensultap), β-cyfloxylate (beta- Cyfluthrin), β-cypermethrin (beta-cypermethrin), Biphenthrin (bifenthrin), metalkamate (bufencarb), Buprofezin (buprofezin), butacarb (butacarb), cadusafos (cadusafos), carbaryl (carbaryl), furadan (carbofuran), carbosulfan (carbosulfan), Padan (cartap), hydrochloric acid Padan (cartap hydrochloride), chlorantraniliprole (chlorantraniliprole), chlorfenapyr (chlorfenapyr), Chlorfenviphos (chlorfenvinphos), UC 62644 (chlorfluazuron), chlormephos (chlormephos), chlopyrifos (chlorpyrifos), chlorpyrifos-methyl (chlorpyrifos-methyl), ring insect amide (chromafenozide), thiophene worm Amine (clothianidin), cyanogen insect amide (cyantraniliprole), cyfloxylate (cyfluthrin), three cyfluthrin chrysanthemums Ester (cyhalothrin), cypermethrin (cypermethrin), decis (deltamethrin), basudin (diazinon), Carbicron (dicrotophos), fluorourea (diflubenzuron), Rogor (dimethoate), dinotefuran (dinotefuran), disulfoton (disulfoton), emamectin benzoate (emamectin), benzoic acid methylamino Avermectin Plain (emamectin benzoate), 5a,6,9,9a-hexahydro-6,9-methano-2,4 (endosulfan), endothion (endothion), endrin (endrin), benzene Sulphur phosphorus (EPN), esfenvalerate (esfenvalerate), etaphos, benzene worm prestige (ethiofencarb), Ethodan (ethion), ethiprole (ethiprole), beneficial fruit (ethoate-methyl), ethofenprox (etofenprox), Nemacur (fenamiphos), fenazaflor (fenazaflor), ethylbenzene prestige (fenethacarb), fenifrothion (fenitrothion), fourth Benzene prestige (fenobucarb), Fenpropathrin (fenpropathrin), fensulfothion (fensulfothion), Entex (fenthion), Entex-ethyl (fenthion-ethyl), fenvalerate (fenvalerate), Frontline (fipronil), flonicamid (flonicamid), Flubendiamide (flubendiamide), flucythrinate (flucythrinate), Dyfonate (fonofos), fufenozide, furathiocarb (furathiocarb), γ-three cyfluthrin chrysanthemum Ester (gamma-cyhalothrin), γ-HCH, halogen ethofenprox (halfenprox), Benzoic acid N-tert-butyl-N-(4-chlorobenzoyl)hydrazide (halofenozide), heptan Worm phosphorus (heptenophos), quinoline prestige (hyquincarb), imidacloprid (imidacloprid), indoxacarb (indoxacarb), Isazofos (isazofos), Telodrin (isobenzan), isocarbophos (isocarbophos), propylamine phosphorus (isofenphos), Propylamine phosphorus-methyl (isofenphos-methyl), Mobucin (isoprocarb), Hosdon (isothioate), isoxathion (isoxathion), kinoprene (kinoprene), λ-Cyhalothrin (lambda-cyhalothrin), Lepimectin, fluorine the third oxygen urea (lufenuron), malathion (malathion), acephatemet (methamidophos) go out more Worm (methomyl), Runner (methoxyfenozide), Menite (mevinphos), Mexacarbate (mexacarbate), milbemycin (milbemectin), Azodrin (monocrotophos), nitenpyram (nitenpyram), Rimon (novaluron), omethoate (omethoate), methomyl (oxamyl), metilomerkaptofosoksid (oxydemeton-methyl), Thiometan (oxydeprofos), Disystom-s (oxydisulfoton), parathion (parathion), parathion-methyl (parathion-methyl), penfluron (penfluron), permethrin (permethrin), phenthoate dimephenthoate cidial (phenthoate), thimet (phorate), zolone (phosalone), phosfolan (phosfolan), phosmet (phosmet), phosphamidon (phosphamidon), the phonetic phosphorus of methylamine (pirimetaphos), anti-aphid Prestige (pirimicarb), pirimiphos ethyl (pirimiphos-ethyl), methyl Actellic (pirimiphos-methyl), acyl Amic metadiazine quinoline (primidophos), Profenofos (profenofos), profluthrin, Carbamult (promecarb), Kayaphos (propaphos), arprocarb (propoxur), Toyodan (prothiofos), pymetrozine (pymetrozine), Pyramat (pyrafluprole), pyridalyl (pyridalyl), pyrifluquinazon, pyridine alcohol (pyriprole), pyriproxyfen (pyriproxyfen), spinetoram (spinetoram), ike enemy (spinosad), spiral shell worm ethyl ester (spirotetramat), Sulfoxaflor (sulfoxaflor), second Toyodan (sulprofos), τ-taufluvalinate (tau-fluvalinate) are double Phenylhydrazide (tebufenozide), tebufenpyrad (tebufenpyrad), Teflubenzuron (teflubenzuron), Tefluthrin (tefluthrin), tetramethylfluthrin, θ-cypermethrin (theta-cypermethrin), thiacloprid (thiacloprid), Diacloden (thiamethoxam), thiophene chlorine phosphorus (thicrofos), thiocyclarn (thiocyclam), oxalic acid Thiocyclarn (thiocyclam oxalate), sulphur sulfate (thiodicarb), thiometon (thiometon), desinsection Bis- (thiosultap), dimehypo-disodium (thiosultap-disodium), the mono- sodium (thiosultap- of dimehypo- Monosodium), thuringiensin (thuringiensin), Tolfenpyrad (tolfenpyrad), Hostathion (triazophos) kill Worm grand (triflumuron) and ζ-cypermethrin (zeta-cypermethrin).Depending on the component presence in invention formulation It is lower using the stability of insecticide compound and the preferred administration mode of compound, these compounds can with it is of the invention Trichloromethyl pyridine preparation is used together.In many cases, can before preparation of the invention is applied to soil or it Compound is applied by any suitable mode afterwards.
The some exemplary fungicides that can be used together with trichloromethyl pyridine preparation of the invention include but unlimited In, tricyclazole (tricyclazole), Rabcide (phthalide), ring propionyl bacterium amine (carpropamide), pyroquilon (pyroquilon), double chlorine zarilamid (diclocymet), fenoxanil (fenoxanil), probenazole (probenazole), Isoprothiolane (isoprothiolane), different rice blast net (iprobenfos), isotianil (isotianil), tiadinil (tiadinil), kasugarnycin (kasugamycin), flutolanil (flutolanil), go out rust Amine (mepronil), Pencycuron (pencycuron), polyoxin (polyoxins), jinggangmeisu (validamycin), Toclophos-methyl, niacinamide (boscalid), pyrrole metsulfovax (penthiopyrad), thiophene fluorine bacterium amine (thifluzamide), bixafen, fluopyram (fluopyram), isopyrazam (isopyrazam), propiconazole (propiconazole), difenoconazole (difenoconazole), benzoxazole (fenbuconazole), kind bacterium azoles (ipconazole), triazolone (triadimefon), hexaconazole (hexaconazole), nitrile Fluoxastrobin (azoxystrobin), Metaminostrobin, orysastrobin (orysastrobin) and Acibenzolar (acibenzolar-S-methyl).These are killed very Some opportunitys in application invention formulation in microbial inoculum may not be effectively, because of fungal disease to disease control when applying It propagates and growth cycle may not be optimal.These fungicides effectively use and the opportunity of applying can be by those skilled in the art Member is readily determined.Depending on using the stability and compound of herbicidal compounds in the presence of the component of invention formulation Preferred administration mode, these compounds can apply together with trichloromethyl pyridine preparation of the invention.In many cases, Compound can be applied by any suitable mode before or after preparation of the invention is applied to soil.
The some exemplary herbicide-safeners that can be used together with trichloromethyl pyridine preparation of the invention include but not It is limited to, benoxacor (benoxacor), benthiocarb (benthiocarb), cloquintocet (cloquintocet-mexyl), herbicide Grand (daimuron), dichlormide (dichlormid), dicyclonon, dimepiperate (dimepiperate), fenchlorazole (fenchlorazole-ethyl), fenclorim (fenclorim), the careless amine (flurazole) of solution, fluxofenim (fluxofenim), Furilazole (furilazole), super quick albumen (Harpin proteins), isoxadifen (isoxadifen-ethyl), Mefenpyrdiethyl (mefenpyr-diethyl), mephenate, oxalane (MG 191), MON 4660, naphthalene dimethyl anhydride (naphthalic anhydride (NA)), oxabetrinil (oxabetrinil), R29148 and N- benzene-sulfonyl yl-benzamide (N-phenyl-sulfonylbenzoic acid amides).Depending on using weeding in the presence of the component of invention formulation The stability of agent safener compound and the preferred administration mode of compound, these compounds can be with three chloromethanes of the invention Yl pyridines preparation is used together.In many cases, can pass through before or after preparation of the invention is applied to soil Any suitable mode applies compound.
The some Exemplary plants growth regulators that can be used together with trichloromethyl pyridine preparation of the invention include but It is not limited to, 2,4- drops (2,4-D), 3,4- Embutoxs (3,4-DB), heteroauxin (IAA), indolebutyric acid (IBA), naphthaleneacetamide (naphthaleneacetamide), methyl α-naphthyl acetate (α-naphthaleneacetic acid), kinetin (kinetin), Ji is listened (zeatin), ethephon (CEPHA),2-(chloroethyl) phosphonic acid (ethephon), aviglycine, 1- methyl cyclopropene (1-MCP), ethephon (CEPHA),2-(chloroethyl) phosphonic acid (ethephon), 92 〇 (gibberellins), gibberellic acid (gibberellic acid), S- abscisic acid (abscisic Acid), ancymidol (ancymidol), flurprimidol (flurprimidol), mefluidide (mefluidide), multiple-effect Azoles (paclobutrazol), tetcyclacis (tetcyclacis), uniconazole P (uniconazole), brassin lactones (brassinolide), ethyl brassinolide (brassinolide-ethyl) and ethylene (ethylene).Depending at this The stability of plant growth regulator compound and the preferred administration mode of compound are used in the presence of the component of invention preparation, These compounds can be used together with trichloromethyl pyridine preparation of the invention.It in many cases, can be will be of the invention Preparation be applied to soil before or after compound applied by any suitable mode.
Exemplary formulation
Embodiment 1: by the way that the trichloromethyl pyridine of technical grade to be dissolved in dicyandiamide solution, preparation includes polar solvent High loading capacity trichloromethyl pyridine SL preparation (360g/L) comprising polar solvent corrosion inhibitor.By solution under IKA mixing Mixing is until solution is substantially uniform.
Referring now to table 1.50 DEG C of temperature different time intervals test all samples metal erosion stability, and by its It is compared with N-serve commercial control preparation.As a result it is shown in Table 1.It is surveyed in the trichloromethyl pyridine preparation of 40ml preparation The corrosion stability of ensaying category coupongs (coupons) (carbon steel (AISI 1018)).Corrosion is immersed by about the 45% of coupongs to survey In the solution of examination.The width of metal sampler piece is about 1.5 inches, length is 3 inches, with a thickness of 1/16 inch to 1/8 inch.? In test process, by any color change or relict sediment on censored sample piece surface, the corruption of coupongs is visually inspected Lose situation.The result of these experiments is summarized in table 1.
Table 1: stablize high three chloromethane of loading capacity comprising polar solvent after carrying out corrosion test with Mild steel coupons piece at 50 DEG C The example composition of yl pyridines SL preparation (360g/L technical grade trichloromethyl pyridine).It compares (N-SERVE) sample (sample 1) Loading capacity be 240g/L.
The common commercial title of solvent: Hallcomid M-8-10:N, N- dimethyl decoyl is obtained commercially obtained in table 1 The mixture of amine (N, N- dimethyl suet amide) and N, N- dimethyldecamide (N, N- dimethyl sheep wax amide)； RhodiaSolv RPDE: the reactive material of dimethyl adipate and dimethyl glutarate and dimethyl succinate；Aromatic 100: solvent naphtha (petroleum), light aromatics；TamiSolve NxG:N- butyl pyrrolidine ketone.
Embodiment 2: prepare material solution of the technical grade trichloromethyl pyridine of 360g/L in triethyl phosphate, and to The additive of specific quantity is added in the solution to limit the corrosion to carbon steel.The solution that a small amount of (about 15mL) is left in glass jar is used In test in room temperature (about 20 DEG C) and -12 DEG C of storage stability.- 12 DEG C of samples are after reaching aging in 24 hours by cold cut It is mixed into a small amount of little particle technical grade trichloromethyl pyridine in liquid to be inoculated with, and the storage temperature for being immediately returned to -12 DEG C carries out Storage.Mild steel coupons piece part is immersed in the solution of 54 DEG C of storages.Any liquid and gas of routine observation coupongs are rotten Lose sign.Observe any inhomogeneities, crystallinity and the mobility in room temperature and -12 DEG C of solution.The display observation situation of table 2 It summarizes.
Table 2:
Embodiment 3: with the cyclopentanone of different ratios or cyclohexanone and Rhodiasolv RPDE (dimethyl glutarate, oneself two The mixture of dimethyl phthalate and dimethyl succinate) mixture prepare uniform group of technical grade trichloromethyl pyridine (360g/L) Close object.A small amount of (about 15mL) solution is left in glass jar for testing in room temperature (about 20 DEG C) and -10 DEG C of storage stability.- 10 DEG C of samples are carried out after reaching aging in 24 hours by being mixed into a small amount of little particle technical grade trichloromethyl pyridine in cold soln Inoculation, and the storage temperature for being immediately returned to -10 DEG C is stored.Any inhomogeneities of the solution of observation different temperatures, Crystallinity and mobility.Any temperature in storage 2 weeks, being not observed in solution has crystal or any other uneven Property.Table 3 shows composition and the summary of their stability.
Table 3:
Corrosion test: prepare original of the 360g/L technical grade trichloromethyl pyridine in cyclohexanone/RPDE (60:40 weight ratio) Expect solution, and adds the corrosion inhibitor of specific quantity into the solution.Using following scheme test acquired solution to carbon steel tank Etching problem.Mild steel coupons piece part is immersed in the solution of 54 DEG C of storages.Any liquid phase of routine observation coupongs and Gaseous corrosion sign.The summary of the display observation situation of table 4.
Table 4:
Embodiment 4: storage stability test: the homogeneous compositions of technical grade trichloromethyl pyridine (360g/L) are dispersed in Left in methoxybenzene solvent, in glass jar a certain amount of about 15mL solution for test in room temperature (about 20 DEG C), 54 DEG C and -7 DEG C storage stability.- 7 DEG C of samples are after reaching aging in 24 hours by being mixed into a small amount of little particle technical grade three in cold soln Chloromethylpyridine is inoculated with, and the temperature for being immediately returned to -7 DEG C is stored.Observe any of the solution of different temperatures Inhomogeneities, crystallinity and mobility.Storage 2 weeks in any temperature, be not observed in solution have crystal or it is any its Its inhomogeneities.
Corrosion test: material solution of the 360g/L technical grade trichloromethyl pyridine in methoxybenzene is prepared, and molten to this The corrosion inhibitor of specific quantity is added in liquid.Using following scheme test acquired solution to the etching problem of carbon steel tank.By carbon steel Coupongs part is immersed in the solution of 54 DEG C of storages.Any liquid and gas signs of corrosion of routine observation coupongs.Table 5 is aobvious Show the summary of observation situation.
Table 5:
Although innovative techniques are described in detail and are described in the drawings and the preceding description, it should be realized that This is illustrative rather than restrictive, it should be understood that only has shown that and describes preferred embodiment, and it is expected to protect Protect all changes and modification carried out in innovative techniques scope.Although in addition, innovative techniques be with specific embodiment, What Theoretical Proof, explanation and explaination were illustrated, but these explanations and subsidiary discussion never should be interpreted that and limit the technology.Institute There is the entire content of the bibliography such as the text quoted in patent, patent application and the application, scientific paper, publication to pass through It is incorporated by the application.

Claims (21)

1. a kind of preparation, it includes:
2- chloro- 6- (trichloromethyl) pyridine, wherein amount of the chloro- 6- of 2- (trichloromethyl) pyridine in the preparation is about 200 to about 400g/L；
At least one polar solvent, is selected from: N, N- dialkyl group fatty acid amide, ketone, dibasic ester, organophosphorus compounds and Alkoxy benzene compound, wherein the polar solvent accounts for the about 40wt% to about 70wt% of the preparation；
At least one corrosion inhibitor, is selected from: liquid epoxies；2,6- lutidines；Epoxy linseed oil；2- ammonia Base-2- methyl-1-propyl alcohol；Methyl nicotinate；Iso methyl nicotinate；And niacinamide；Wherein the corrosion inhibitor each accounts for about 0.5wt% to about 2.5wt%；With
Second solvent, is selected from: solvent naphtha, arsol, mineral oil, kerosene and dimethylbenzene, wherein second solvent Account for the about 5.0wt% to about 20.0wt% of the preparation.
2. the preparation of claim 1, wherein the ketone is cyclopentanone and cyclohexanone.
3. the preparation of claim 1, wherein the dibasic ester includes:
The diester of formula (IIa):
(IIa)；
The diester of formula (IIb):
(IIb)；With
The diester of formula (IIc):
(IIc),
Wherein R1And R2Separately include the hydrocarbon with 1 to about 8 carbon atom.
4. the preparation of claim 1, wherein the organophosphorus compounds is selected from: triethyl phosphate, tricresyl phosphate (isobutyl group) Ester, tributoxyethyl phosphate and tri-2-ethylhexyl phosphate.
5. the preparation of claim 1, wherein the alkoxy benzene compound is methoxybenzene or ethoxybenzene.
6. the preparation of claim 1, it includes:
About 250 to about 300g/L 2- chloro- 6- (trichloromethyl) pyridine；
About 40 to about 60wt% N, N- dimethyloctanamide (N, N- dimethyl suet amide) and N, N- dimethyldecamide (N, N- dimethyl sheep wax amide) mixture；
About 0.5 to about 1.5wt% liquid epoxies and about 0.5 to about 1.5wt% 2,6- lutidines；With
About 5 to about 20wt% solvent naphtha.
7. the preparation of claim 1, it includes:
About 230 to about 300g/L 2- chloro- 6- (trichloromethyl) pyridine；
About 45 to about 55wt% N, N- dimethyloctanamide (N, N- dimethyl suet amide) and N, N- dimethyldecamide (N, N- dimethyl sheep wax amide) mixture；
About 0.75 to about 1.4wt% liquid epoxies；
About 0.5 to about 1.5wt% 2,6- lutidines；With
About 10 to about 15wt% solvent naphtha.
8. preparation according to claim 1, it includes:
The 2- of about 240g/L chloro- 6- (trichloromethyl) pyridine；
About 50.0 to about 55wt% N, N- dimethyloctanamide (N, N- dimethyl suet amide) and N, N- dimethyldecamide The mixture of (N, N- dimethyl sheep wax amide)；
About 1.0 to about 1.1wt% liquid epoxies oil；
About 0.5 to about 1.5wt% 2,6- lutidines；With
About 11.0 to about 14.0wt% solvent naphtha.
9. the preparation of claim 1, it includes:
The 2- of about 240g/L chloro- 6- (trichloromethyl) pyridine；
The N of about 50.55wt%, N- dimethyloctanamide (N, N- dimethyl suet amide) and N, N- dimethyldecamide (N, N- Dimethyl sheep wax amide) mixture；
The liquid epoxies oil of about 1.2wt%；
About 0.5 to about 1.5wt% 2,6- lutidines；With
The solvent naphtha of about 12.64wt%.
10. the preparation of claim 1, it includes:
About 200 to about 400g/L 2- chloro- 6- (trichloromethyl) pyridine；
About 20 to about 50wt% dibasic ester；
About 0.5 to about 2.5wt% epoxy linseed oil；
About 0.5 to about 2.5wt% niacinamide；With
About 20.0 to about 50.0wt% cyclohexanone.
11. the preparation of claim 1, it includes:
The 2- of about 240g/L to about 350g/L chloro- 6- (trichloromethyl) pyridine；
About 20 to about 40wt% dibasic ester；
About 1.5 to about 2.5wt% epoxy linseed oil；
About 0.5 to about 1.5wt% niacinamide；With
About 25.0 to about 45.0wt% cyclohexanone.
12. the preparation of claim 1, it includes:
The 2- of about 240g/L chloro- 6- (trichloromethyl) pyridine；
The dibasic ester of about 50.47wt%；
The epoxy linseed oil of about 1.5wt%；
The niacinamide of about 0.8wt%；With
The cyclohexanone of about 12.62wt%.
13. the preparation of claim 1, it includes:
About 200 to about 400g/L 2- chloro- 6- (trichloromethyl) pyridine；
About 40 to about 60wt% dibasic ester；
About 0.5 to about 2.5wt% epoxy linseed oil；With
About 0.4 to about 1.5wt% niacinamide.
14. the preparation of claim 1, it includes:
The 2- of about 240g/L chloro- 6- (trichloromethyl) pyridine；
The dibasic ester of about 63.08wt%；
The epoxy linseed oil of about 1.5wt%；With
About 0.6 to about 1.0wt% niacinamide.
15. the preparation of claim 1, it includes:
The 2- of about 240g/L chloro- 6- (trichloromethyl) pyridine；
The dibasic ester of about 63.08wt%；
The epoxy linseed oil of about 1.5wt%；With
The niacinamide of about 0.8wt%.
16. a kind of preparation, it includes:
The 2- of about 324g/L chloro- 6- (trichloromethyl) pyridine；
The dibasic ester of about 26.02wt%；
The epoxy linseed oil of about 2.04wt%；
The niacinamide of about 0.98wt%；With
The cyclohexanone of about 39.02wt%.
17. a kind of preparation, it includes:
The preparation of claim 16；With
At least other agricultural ingredients, are selected from: herbicide, insecticide, nematicide, fungicide and fertilizer.
18. the preparation of claim 17, wherein the agricultural ingredients are fertilizer.
19. the preparation of claim 18, wherein the fertilizer includes nitrogen.
20. a kind of method for handling soil comprising following steps:
The preparation of claim 19 is administered to at least one region selected from following region: the surface of a part of soil, soil Under the surface of a part of earth, a part of plant, and a part on the surface adjacent with plant.
21. the method for claim 20, wherein the step of applying includes that the preparation is injected into a part of soil.
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Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
US20200102255A1 (en) 2017-06-14 2020-04-02 Basf Se New method for fertilizing agricultural soil
CA3169007A1 (en) * 2020-02-26 2021-09-02 Janice PALETTA Non-corrosive formulation composition for nitrogen inhibitors

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090007616A1 (en) * 2007-07-06 2009-01-08 Bureman Phillip E Method of inhibiting corrosion on ferrous metal surfaces in contact with nitrogen fertilizer solutions
CN102548395A (en) * 2009-09-16 2012-07-04 巴斯夫欧洲公司 Method for reducing nitrous oxide emission from soils
CN102617254A (en) * 2012-04-01 2012-08-01 廊坊北鑫化工有限公司 Emulsion in water for enhancing efficacy of nitrogen fertilizer, and application of emulsion in water

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6699829B2 (en) * 2002-06-07 2004-03-02 Kyzen Corporation Cleaning compositions containing dichloroethylene and six carbon alkoxy substituted perfluoro compounds
GB0621440D0 (en) * 2006-10-27 2006-12-06 Syngenta Crop Protection Ag Herbicidal compositions
US8741805B2 (en) * 2007-01-22 2014-06-03 Dow Agrosciences, Llc. Enhanced nitrification inhibitor composition
WO2009065906A2 (en) * 2007-11-20 2009-05-28 Cognis Oleochemicals Gmbh Method for producing an organic composition containing an n-nonyl ether
CN102249817B (en) * 2011-04-21 2013-08-28 浙江奥复托化工有限公司 Preparation for inhibiting soil nitrogen loss as well as preparation method and application thereof
KR101972357B1 (en) * 2012-01-09 2019-04-29 더 케무어스 컴퍼니 에프씨, 엘엘씨 Aqueous binder solutions
PL2885261T3 (en) * 2012-08-15 2019-10-31 Koch Agronomic Services Llc Liquid compositions containing urease inhibitors and glycol alkyl ethers
CA2881711A1 (en) * 2012-08-15 2014-02-20 Koch Agronomic Services, Llc Liquid compositions containing urease inhibitors and aryl alkyl alcohols
EP2925727A1 (en) * 2012-11-30 2015-10-07 Bayer CropScience AG (r) enantiomers of carboxamides for controlling of harmful microorganisms or for enhancing plant health

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090007616A1 (en) * 2007-07-06 2009-01-08 Bureman Phillip E Method of inhibiting corrosion on ferrous metal surfaces in contact with nitrogen fertilizer solutions
CN102548395A (en) * 2009-09-16 2012-07-04 巴斯夫欧洲公司 Method for reducing nitrous oxide emission from soils
CN102617254A (en) * 2012-04-01 2012-08-01 廊坊北鑫化工有限公司 Emulsion in water for enhancing efficacy of nitrogen fertilizer, and application of emulsion in water

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
左景伊 等: "《腐蚀数据与选材手册》", 31 October 1995, 化学工业出版社 *
李进军等: "《绿色化学导论》", 31 August 2015, 武汉大学出版社 *
赵俊会: "《高分子化学与物理》", 28 February 2010, 中国轻工业出版社 *
陈冠荣: "《化工百科全书》", 30 September 1994, 化学工业出版社 *

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