TWI816139B - 用於增強氮穩定劑之組合物之調配系統 - Google Patents
用於增強氮穩定劑之組合物之調配系統 Download PDFInfo
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- TWI816139B TWI816139B TW110121952A TW110121952A TWI816139B TW I816139 B TWI816139 B TW I816139B TW 110121952 A TW110121952 A TW 110121952A TW 110121952 A TW110121952 A TW 110121952A TW I816139 B TWI816139 B TW I816139B
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- nitrogen
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 481
- 239000000203 mixture Substances 0.000 title claims abstract description 478
- 238000009472 formulation Methods 0.000 title claims abstract description 283
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 253
- 239000003381 stabilizer Substances 0.000 title claims abstract description 171
- 230000002708 enhancing effect Effects 0.000 title 1
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- 239000000126 substance Substances 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 153
- 150000008064 anhydrides Chemical class 0.000 claims description 142
- 239000003337 fertilizer Substances 0.000 claims description 128
- -1 ethylene, propylene, butyl alkenes Chemical class 0.000 claims description 108
- 230000000087 stabilizing effect Effects 0.000 claims description 97
- 238000000034 method Methods 0.000 claims description 86
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- 239000002601 urease inhibitor Substances 0.000 claims description 76
- 239000003112 inhibitor Substances 0.000 claims description 73
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 63
- 229940090496 Urease inhibitor Drugs 0.000 claims description 56
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 48
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
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- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 claims description 8
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 8
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
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- PDNZJLMPXLQDPL-UHFFFAOYSA-N (1-aminocyclopentyl)methanol Chemical compound OCC1(N)CCCC1 PDNZJLMPXLQDPL-UHFFFAOYSA-N 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 4
- TXJYONBSFGLSSF-UHFFFAOYSA-N 1-(diethylamino)propane-1,2-diol Chemical compound CCN(CC)C(O)C(C)O TXJYONBSFGLSSF-UHFFFAOYSA-N 0.000 claims description 4
- PCXJASANFWPUMO-UHFFFAOYSA-N 1-(methylamino)propan-1-ol Chemical compound CCC(O)NC PCXJASANFWPUMO-UHFFFAOYSA-N 0.000 claims description 4
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
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- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 claims description 4
- DIORNGPTUKJRHG-UHFFFAOYSA-N 1-aminobutane-1,4-diol Chemical compound NC(O)CCCO DIORNGPTUKJRHG-UHFFFAOYSA-N 0.000 claims description 3
- RILLZYSZSDGYGV-UHFFFAOYSA-N 2-(propan-2-ylamino)ethanol Chemical compound CC(C)NCCO RILLZYSZSDGYGV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/02—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
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- C05C9/00—Fertilisers containing urea or urea compounds
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Abstract
本發明所揭示之標的物係關於含有氮穩定劑組分及有機酸酐組分以及非質子性溶劑及胺穩定劑之氮穩定組合物的調配物。本文所揭示之調配物展現許多有益特性,諸如個別組分在高濃度下之溶解度增加以及易於提高的調配物之化學熱穩定性。
Description
本發明所揭示之標的物係關於含有氮穩定劑及有機酸酐及其調配物之組合物。進一步描述該等組合物及調配物在農業中提高養分吸收及抑制硝化及/或脲酶活性之用途。
氮係一種必需的植物營養素,認為其對於充足且茂盛的簇葉而言係重要的。脲提供高氮含量且為主要氮肥。在土壤水分存在下,天然或合成脲轉化為銨離子,其隨後可用於植物吸收。銨可以經由硝化過程由土壤中之細菌進一步轉化為硝酸鹽。硝酸鹽亦可用於植物吸收。然而,植物之脲使用效率低。
實務上,氮肥往往僅在生長季節開始時施用一次。通常,氮肥係調配為乾燥顆粒、球粒或由脲單獨或與硝酸銨混合為UAN(含有脲、硝酸銨及水之混合物)構成的流體。脲亦存在於動物糞肥中。此等形式之脲具有顯著缺點,因為其在施用於土壤時經歷快速分解且產生氨氣。此係由於土壤中存在脲酶,脲酶與脲反應產生碳酸氫銨及氨。此組一般過程在此項技術中稱為揮發。揮發導致氮肥使用效率降低、產量降低、植物出現氮缺乏症狀、難聞的氣味以及可能有害的氨氣濃度。此外,產生之氨亦可以藉由土壤中之細菌轉化為硝酸鹽,其稱為硝化。過量硝酸鹽可以藉由土壤中之某些類型的細菌轉化為一
氧化氮或氧化亞氮,其稱為脫氮作用(denitrification)。
已開發出能夠延遲氮肥降解之硝化及/或脲酶抑制劑(通常稱為氮穩定劑),從而減少了在不存在此等抑制劑之情況下否則將發生的含氮降解產物損失。硝化及/或脲酶抑制劑與氮肥組合使用往往會增加氮源保留在土壤中且可供植物吸收之時間量,因而增加肥料之有效性,對作物產量及品質產生積極影響。然而,與成本、安全性、便利性及穩定性相關之問題限制了此等類型之抑制劑的使用。例如,當前產品含有昂貴的有機溶劑,且液體調配物中抑制劑之組成百分比低。此使得必需以更大百分比施用此等液體分散系統,因此使得其使用不經濟且效率低下。此等產品包括例如來自生態農業資源(Eco Agro Resources)之NEONTM產物家族,其中NBPT及DCD以低濃度調配於有機溶劑中。
特定言之,含有NBPT與DCD之組合的商業農業產品展現出各種缺點。歸因於其在水性溶劑中以及提供在高濃度下含有NBPT及DCD之調配物的大量有機溶劑中之低溶解度,已證實為具有挑戰性的且仍然為正在進行之改良領域。商業農業產品之當前調配物含有大量有機溶劑以便適當地調配NBPT及DCD。通常此等調配物採用展現難聞氣味之有機溶劑(諸如二甲亞碸),且因此使用者友好性較低且在本領域中更難以處理。此外,具有大量有機溶劑之此等產品之調配物亦已展示對環境及野生動物展現負面影響。
因此,非常需要找到經濟的遞送調配物,其對環境及動物安全,且含有可直接施用於液態肥料(諸如UAN)之硝化抑制劑及脲酶抑制劑之適當平衡及濃度。因此,儘管進行了持續不斷的研究工作以改良現有產品,但此項技術中仍大量需要開發含有氮穩定劑以有效控制酶誘導之脲分解的更好組合物及調配物。
在一個態樣中,本文所描述之主題係關於一種穩定調配物,其包含:包含氮穩定劑組分之氮穩定組合物;有機酸酐組分,其中氮穩定劑組分為脲酶抑制劑及/或硝化抑制劑;非質子性溶劑;及胺穩定劑。在一些實施例中,氮穩定劑組分為N-(正丁基)硫代磷酸三醯胺(NBPT)及/或二氰胺(DCD)。在一些實施例中,有機酸酐組分為有機酸酐聚合物。在一些實施例中,非質子性溶劑為DMSO。在一些實施例中,胺穩定劑為單甲醇胺。
另一態樣係關於農業組合物,其包含如本文所揭示之穩定調配物及肥料。
另一態樣係關於一種抑制土傳脲酶之方法,該方法包含以下步驟:將如本文所揭示之穩定調配物施用至土壤,該調配物以足以抑制由土傳脲酶之作用引起的脲分解之量存在。
另一態樣係關於一種對土壤施肥之方法,該方法包含以下步驟:將如本文中所揭示之穩定調配物或如本文中所揭示之農業組合物施用至土壤。
另一態樣係關於一種製備如本文所揭示之穩定調配物之方法,該方法包含以下步驟:將有機酸酐組分與第一非質子性溶劑混合以形成有機酸酐組分預混合溶液;取出有機酸酐組分預混合溶液之等分試樣;用第二非質子性溶劑稀釋所取出之等分試樣以得到有機酸酐溶液;使有機酸酐溶液與胺穩定劑接觸以得到穩定有機酸酐溶液;及向穩定有機酸酐溶液中添加氮穩定劑組分以得到所需穩定調配物。
此等及其他態樣將在下文中進一步詳細描述。
[圖1]展示實地研究之結果,其中用無脲、含脲肥料及如本文所揭示之含脲肥料調配物(以調配物之總重量計,具有15% NBPT、5% DCD及5%有機酸酐聚合物6 w/w)處理玉米場。圖1中之A組展示未經處理之玉米穗軸(左側玉米穗軸);用氮肥脲處理的玉米穗軸(中間玉米穗軸)及用如本文所揭示之調配物15-5-5與脲組合處理的玉米穗軸(右側玉米穗軸)。各玉米穗軸上之列數增加如下:未經處理之玉米穗軸>經脲處理之玉米穗軸>經脲/調配物處理之玉米穗軸。圖1中之組B展示未經處理(左側玉米穗軸)、用氮肥脲(中間玉米穗軸)處理且用脲與所揭示之調配物15-5-5(右側玉米穗軸)組合處理之玉米穗軸。每個玉米穗軸中顆粒之列數隨著未經處理之玉米穗軸>經脲處理之玉米穗軸>經脲/調配物處理之玉米穗軸而增加。
[圖2]為展示實地研究之收穫結果的條形圖,其中採用氮施肥與所揭示之調配物組合處理在無耕作下生長之玉米植物。未進行不同處理(P1-P9)且與未經處理之植物或用氮肥脲處理之植物相比。
[圖3]為展示在左側的未經處理之玉米穗軸及在右側的用氮肥脲(135kg/ha N)處理之玉米穗軸的圖像。未經處理之玉米展示N供應不足/不充分導致顆粒畸形(流產),而經處理之玉米穗軸展現增加量之核。
[圖4]為展示在左側的未經處理之玉米穗軸及在右側的用如本文所揭示之調配物與氮肥脲(135kg/ha N)組合處理之玉米穗軸的圖像。未經處理之玉米展示N供應不足/不充分導致顆粒畸形(流產),而經處理之玉米穗軸展示N在整個生長週期中之充分供應維持植物中之蛋白質含量,其擔負顆粒之形成及填充。
[圖5]為展示用氮肥脲與如本文所揭示之調配物(P)組合處理之玉米穗軸(參見左側玉米穗軸)的圖像;未經處理之玉米穗軸(參見中間玉米穗軸);及用氮肥脲處理之玉米穗軸(參見右側玉米穗軸)。用如本文所揭示
之調配物與氮肥脲組合處理之玉米穗軸在穗軸上展現大部分列的玉米。
[圖6]為展示用氮肥脲與如本文所揭示之調配物(P)組合處理之玉米穗軸(參見左側玉米穗軸)及用氮肥脲處理之玉米穗軸(參見右側玉米穗軸)的圖像。用如本文所揭示之調配物與氮肥脲組合處理之玉米穗軸在穗軸上展現大部分列的玉米。
現將在下文中更充分地描述本發明所揭示之主題。然而,得益於在前述描述中所呈現之教示內容,熟習關於本發明所揭示之主題的技術者將想到本文中所闡述之本發明所揭示之主題之許多修改及其他實施例。因此,應理解,本發明所揭示之主題不限於所揭示之具體實施例且修改及其他具體實施例意欲包括於所附申請專利範圍之範疇內。換言之,本文所描述之主題覆蓋所有替代方案、修改及等效物。在所併入之文獻、專利及類似材料中之一或多者(包括(但不限於)定義術語、術語用法、所描述之技術等)與本申請案不同或抵觸的情況下,以本申請案為準。除非另外定義,否則本文所使用之所有技術及科學術語均具有與一般熟習此項技術者中之一者通常理解相同之含義。本文所提及之所有公開案、專利申請案、專利及其他參考文獻均以全文引用的方式併入本文中。
如上所述,脲為廣泛用於農業生產之主要氮肥中之一者。咸信若不正確地施用,則作為脲施用之氮最多會損失40%,因為在田間施用後,其可以經由脲酶與水反應以形成碳酸銨。碳酸銨不穩定且分解為二氧化碳及氨,其可以揮發且散失至空氣中。損失可能為重大的,且取決於多種因素,諸如土壤pH、土壤溫度、土壤濕度、土壤之陽離子交換能力及土壤有機物含量。
已開發或提出許多控制自脲之揮發性氮損失之方法,包括應用
銅及鋅之金屬鹽、硼化合物、有機脲酶抑制劑、酸塗層、聚合物塗層及脲與醛反應以形成反應加成物。舉例而言,N-(丁基)硫代磷酸三醯胺(NBPT)係全世界農業中最知名的脲酶抑制劑之一。不幸的係,NBPT在其使用中面臨各種缺點。舉例而言,NBPT極難以處理,此係因為其無法以其固體形式使用之黏性、蠟質、熱及水敏感性材料,因為其以低濃度使用,使得其難以在固體含脲組合物(例如,球粒(亦即,大顆粒))上及在土壤中均勻分佈。為了將NBPT均勻分佈至固體含脲組合物上,NBPT應在噴灑至固體含脲組合物上之前分散至載劑中。因此,含有NBPT的溶劑系統之使用係合乎需要的,因為在其液體形式中,溶劑系統能夠將NBPT分佈成顆粒脲(例如,脲球粒)且分佈成含有脲之液體肥料。藉由將NBPT引入溶劑系統中之含有脲(例如,脲硝酸銨溶液或UAN)的液體肥料中,NBPT更充分地分散於液體肥料中。此外,NBPT為熱不穩定的且在與水及酸接觸時分解。此尤其在通常達至超過35℃之溫度且有時可以達至高達45℃或更高之農田(例如玉米田地、小麥田地等)中觀測到。一旦分解,NBPT在對脲酶提供所需抑制作用中無效。因此,降低NBPT之損失及分解速率,進而可提高其在土壤中之功效的調配物在減少化合物自身之負面環境影響中將具有極大價值。
二氰二胺為通常用於農業應用中之硝化抑制劑,例如最終用途肥料組合物。如同脲酶抑制劑,二氰二胺具有若干缺點。硝化抑制劑,諸如二氰二胺,通常在水中具有極低溶解度(約41公克/公升(「公克/公升」))。因此,難以將硝化抑制劑併入至水性最終用途肥料組合物中,尤其在田地條件下。因此,在水中以低濃度使用硝化抑制劑,諸如二氰二胺,使得難以將硝化抑制劑均勻分佈至固體含脲組合物,諸如球粒(亦即,大顆粒)上及土壤中。為了將二氰二胺均勻分佈至含脲球粒或顆粒上,二氰二胺應在噴灑至脲上之前將分散於溶劑載劑中。因此,使用含有二氰二胺之溶劑系統(本文中亦稱為
「DCD」)係合乎需要的,因為在其液體形式中,溶劑系統能夠將二氰二胺分佈至脲顆粒或球粒、脲硝酸銨顆粒或球粒或除此以外的含脲顆粒或球粒,且分佈至含有脲或脲硝酸銨之液體肥料中。藉由將二氰二胺胺引入溶劑系統中之含有脲(例如,脲硝酸銨溶液或UAN)之液體肥料中,DCD能夠較好地分散於液體肥料中。
有利的係,已展示本文中所描述之組合物、調配物及方法藉由在如本文所揭示之特定溶劑系統中用有機酸酐調配此等氮穩定劑而為農業中之氮穩定劑(諸如NBPT及/或DCD)之使用提供期望特性。將此等氮穩定劑與有機酸酐組合於所揭示之溶劑系統(亦稱為「媒劑」)中已提供展現各種有利特性之調配物,諸如(但不限於)延長之熱/化學/酶穩定性、增加之存放期、降低之揮發性、降低之施用速率、改良之黏度、不存在任何強烈難聞的臭味或氣味、製備簡易性、操作簡易性、脲酶及硝化抑制之延長/長期作用,以及極佳環境及毒理學概況。
不受理論束縛,但咸信有機酸酐提供對氮穩定劑之穩定作用,其使得熱、化學及/或酶穩定性得以改良,從而減少氮穩定劑之分解。此外,如本文所揭示之媒劑允許在高濃度下對氮穩定劑及有機酸酐進行溶合。此提供一種調配物,其在與目前可商購之調配物氮穩定劑相比時展現改良之熱及化學穩定性、減少的臭味及額外有益特性。
因此,本文所揭示之組合物不僅有助於增加氮穩定劑可用性,且亦有助於延長其發揮有效氮穩定劑之效能的壽命。
定義
如本文所使用,術語「雜芳基」係指包含至少五員或六員不飽和及共軛芳族環之基團,該環含有至少兩個環碳原子及一至四個選自氮、氧及/或硫之環雜原子。熟習此項技術者常常可替代地將該等雜芳基稱為「雜芳族
基」。在一些實施例中,雜芳基在雜芳基環中具有二至十二個碳原子,或者四至五個碳原子。實例包括但不限於吡啶基、嘧啶基、吡基、吡咯基、呋喃基、四唑基、異唑基、二唑基、苯并噻吩基、苯并呋喃基、喹啉基、異喹啉基及其類似物。
如本文所使用,術語「芳基」係指包含至少一個類似於六員苯環之不飽和及共軛六員環之基團。具有該等不飽和及共軛環之芳基亦作為「芳族」基團為熟習此項技術者已知。在一些實施例中,芳基具有6至12個環碳。芳基包括但不限於包含苯基及萘基環基團之芳族基團。
如本文所使用,術語「經取代」係指部分(諸如雜芳基、芳基、烷基及/或烯基),其中該部分鍵結至一或多個額外有機或無機取代基。在一些實施例中,經取代之部分包含1、2、3、4或5個額外取代基或自由基。適合的有機及無機取代基包括(但不限於)羥基、環烷基、芳基、經取代之芳基、雜芳基、雜環、經取代之雜環、胺基、經單取代之胺基、經二取代之胺基、醯氧基、硝基、氰基、羧基、烷氧羰基、烷基甲醯胺、經取代之烷基甲醯胺、二烷基甲醯胺、經取代之二烷基甲醯胺、烷基磺醯基、烷基亞磺醯基、硫烷基、烷氧基、經取代之烷氧基或鹵代烷氧基,其中該等術語在本文中定義。除非本文另外規定,否則有機取代基可以包含1至4個或5至8個碳原子。當經取代之部分藉由超過一個取代基鍵結至其上時,則取代基可相同或不同。
如本文所使用,術語「未經取代」係指如上文所描述之不鍵結至一或多個額外有機或無機取代基之部分(諸如雜芳基、芳基、烯基及/或烷基),意謂該部分僅僅經氫取代。
如本文所使用,術語「鹵基」、「鹵素」或「鹵化物」係指氟、氯、溴或碘原子或離子。
如本文所使用,術語「烷氧基」係指經由單一末端醚鍵鍵結之
烷基;亦即,「烷氧基」基團可以定義為-OR,其中R為如上文所定義之烷基。實例包括但不限於甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、三級丁氧基、異丁氧基、二級丁氧基及其類似基團。
如本文所使用,術語「經取代之烷氧基」係指如上文所定義之烷氧基,其具有一個、兩個或多於兩個鍵結至烷基之額外有機或無機取代基。適合的有機及無機取代基包括但不限於羥基、環烷基、胺基、經單取代之胺基、經二取代之胺基、醯氧基、硝基、氰基、羧基、烷氧羰基、烷基甲醯胺、經取代之烷基甲醯胺、二烷基甲醯胺、經取代之二烷基甲醯胺、烷基磺醯基、烷基亞磺醯基、硫代烷基、硫代鹵烷基、烷氧基、經取代之烷氧基或鹵烷氧基。當烷氧基之烷基藉由超過一個取代基鍵結至其上時,則取代基可相同或不同。
如本文所使用,術語「胺基」係指藉由用取代基取代氨之一或多個氫原子而與氨(NH3)結構上相關之經取代或未經取代之三價含氮基團(radical/group)。
如本文所使用,術語「經單取代之胺基」係指經一個選自烷基、經取代之烷基或芳烷基之基團取代的胺基,其中該等術語具有本文中所見之相同定義。
如本文所使用,術語「經二取代之胺基」係指經兩個選自芳基、經取代之芳基、烷基、經取代之烷基或芳基烷基的可相同或不同的基團取代之胺基,其中該等術語具有如本文所揭示之相同之定義。實例包括但不限於二甲胺基、甲基乙胺基、二乙胺基及其類似物。存在之兩個取代基可相同或不同。
如本文所使用,術語「鹵烷基」係指如上文所定義之烷基,其經一或多個鹵素(諸如氟、氯、溴或碘)取代。實例包括但不限於三氟甲基、
五氟乙基及其類似基團。
如本文所使用,術語「鹵代烷氧基」係指如上文所定義之鹵烷基,其直接鍵結至氧以形成三氟甲氧基、五氟乙氧基及其類似物。
如本文所使用,術語「醯基」指示含有羰基(-C(O)-R基)之基團,其中R基為氫或具有1至8個碳。實例包括但不限於甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、己醯基、庚醯基、苯甲醯基及其類似物。
如本文所使用,術語「醯氧基」係指含有羧基(-O-C(O)-R)基團之基團,其中R基包含氫或1至8個碳。實例包括但不限於乙醯氧基、丙醯氧基、丁醯氧基、異丁醯氧基、苯甲醯氧基及其類似物。
如本文所使用,術語「烷基」係指含有1至8個、1至6個、1至4個或5至8個碳之飽和烴基。在一些情況下,烷基係指含有超過8個碳之飽和烴基。烷基在結構上與非環狀烷烴化合物類似,該非環狀烷烴化合物藉由將一個氫自非環狀烷烴除去及對其進行非氫基團或自由基取代而改質。烷基自由基可以為分支鏈或未分支鏈的。低級烷基自由基具有1至4個碳原子。高級烷基自由基具有5至8個碳原子。烷基、低碳烷基及高碳烷基基團之實例包括但不限於甲基、乙基、正丙基、異丙基、正丁基、二級丁基、三級丁基、戊基、三級戊基、正戊基、正己基、異辛基及其類似基團。
如本文所使用,術語「烯基」係指含有2至8個、2至6個、2至4個或5至8個碳及至少一個碳-碳雙鍵之不飽和烴基。在一些情況下,烯基係指含有超過8個碳之不飽和烴基。不飽和烴基類似於如上文所定義之烷基,亦包含至少一個碳-碳雙鍵。實例包括但不限於乙烯基、烯丙基、2-丁烯基、3-丁烯基、2-戊烯基、3-戊烯基、4-戊烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、2-庚烯基、3-庚烯基、4-庚烯基、5-庚烯基、6-庚烯基及其類似物。術語「烯基」包括具有直鏈及分支鏈之二烯及三烯。
如本文所使用,術語「單環」係指含有單原子環之分子結構,諸如苯或環丙烷。
如本文所使用,術語「雙環」係指含有兩個稠合在一起的原子環之分子結構,諸如萘。
如本文所使用,術語「三環」係指含有稠合在一起的三個原子環之分子結構。
如本文所使用,「氮穩定劑」係指意欲經由對土壤細菌之作用來防止或阻礙硝化、反硝化、氨揮發或脲酶生產過程的任何物質或物質混合物。
如本文所使用,「硝化抑制劑」係指化合物抑制氨氧化成亞硝酸鹽/硝酸鹽之特性。
如本文所使用,術語「脲酶抑制劑」係指化合物抑制脲酶之活性的特性。抑制可以如本文別處所描述來定量。
如本文所使用,術語「熱穩定性」係指當在給定時段內曝露於熱刺激時物質之穩定性。熱刺激之實例包括但不限於自電源產生之熱量及/或自太陽產生之熱量。
如本文所使用,術語「化學穩定性」係指當曝露於諸如空氣(其可以引起氧化)、光(例如日光)、水分/濕度(來自水)、熱(來自陽光),及/或化學劑之外部作用時物質對結構改變之抗性。例示性化學劑包括但不限於可以降解所關注化合物(例如所揭示之聚陰離子聚合物)之結構完整性的任何有機或無機物質。
如本文所使用,術語「酶穩定性」係指物質對外部生物有機體分解物質(例如所揭示之陰離子聚合物)之結構穩定性的抗性。例示性生物有機體包括但不限於土壤中存在之細菌及微生物。
如本文所使用,術語「有效量」係指足以達成如下所描述之硝
化抑制及/或脲酶抑制的氮穩定組合物之量及/或穩定組合物中各組分(亦即,氮穩定劑組分及/或有機酸酐組分)之量。下文給出關於待使用之量、施用方式及適合比率之更多例示性資訊。熟習此項技術者充分瞭解此量可以在廣泛範圍內變化且取決於各種因素,例如天氣、靶物種、部位、施用模式、土壤類型、經處理之培養植物或物質及氣候條件這一實情。
如本文所使用,術語「土壤」應理解為出現於土地表面上之包含生命(例如微生物(諸如細菌及真菌)、動物及植物)及非生命物質(例如礦物質及有機物(例如呈不同分解程度之有機化合物)、液體及氣體)的天然物體,且其特徵在於由於各種物理、化學、生物及人為方法而可與原始物質區分的土壤層。根據農業觀點,土壤主要視為植物(植物環境)之固定物及主要養分基礎。
如本文所使用,術語「肥料」應理解為施用以促進植物及水果生長之化合物。肥料通常經由土壤(用於由植物根部吸收)或藉由葉面供給(用於由葉片吸收)來施用。術語「肥料」可以再分為兩種主要類別:a)有機肥料(由腐爛植物/動物物質組成)及b)無機肥料(由化學物質及礦物質組成)。有機肥料包括糞肥、漿料、蚯蚓堆肥、泥炭、海藻、生活污水及鳥糞。綠色糞肥作物亦定期生長以添加養分(尤其氮)至土壤。製造的有機肥料包括堆肥、血粉、骨粉及海藻提取物。其他實例為酶促分解蛋白質、魚粉及羽毛粉。來自先前年度之分解農作物殘餘物為肥沃度之另一來源。此外,諸如磷礦石、硫酸鉀及石灰石的天然存在之礦物質亦視為無機肥料。無機肥料通常經由化學方法(諸如哈柏-波希法(Haber-Bosch process)),亦使用天然存在之沈積但化學上改變其(例如濃縮三過磷酸鈣)來製造。天然存在之無機肥料包括智利(Chilean)硝酸鈉、磷礦石及石灰石。
如本文所使用,術語「糞肥」為在農業中用作有機肥料之有機
物。視其結構而定,糞肥可以劃分成液體糞肥、半液體糞肥、穩定或固體糞肥及稻草糞肥。視其來源而定,糞肥可以劃分成來源於動物或植物之糞肥。動物糞肥之常見形式包括糞便、尿液、農場漿料(液體糞肥)或堆肥(FYM),然而FYM亦含有一定量之植物物質(通常稻草),其可能已用作動物之墊料。可以使用之糞肥來自以下動物,包含馬、牛、豬、羊、雞、火雞、兔,及來自海鳥及蝙蝠之鳥糞。當用作肥料時,動物糞肥之施用率高度取決於來源(動物類型)。植物糞肥可來源於任何種類之植物,然而亦可明確地出於耕種植物之目的而種植植物(例如豆科植物),從而改良土壤之結構及肥沃度。此外,用作糞肥之植物物質可包括屠宰反芻動物之瘤胃的內含物、廢啤酒花(釀造啤酒所殘留)或海藻。
如本文所使用,術語「種子」包含所有類型之種子,諸如(例如)玉米、種子、水果、塊莖、苗木及類似形式。所使用之種子可以為上文所提及之適用植物的種子,且亦可為基因轉殖植物或藉由通常的培育方法所獲得之植物之種子。
貫穿本說明書及申請專利範圍,字組「包含(comprise/comprises/comprising)」以非排他性意義使用,除非上下文另外要求且與「包括」、「含有」或「其特徵在於」同義,此意謂其為開放式的且不排除額外未敍述之要素或方法步驟。
如本文所使用,過渡片語「基本上由...組成」將申請專利範圍之範疇限制於所規定材料或步驟「及實質上不影響所主張本發明所揭示之標的物之基礎及新穎特徵的彼等材料或步驟」。
如其中所使用,過渡片語「由......組成」排除申請專利範圍中未規定之任何要素、步驟或成分。
如本文所使用,術語「約」當提及值時意謂涵蓋相對於規定量
在一些實施例中±5%、在一些實施例中±2%、在一些實施例中±1%、在一些實施例中±0.5%且在一些實施例中±0.1%之變化,因為此類變化適合於執行所揭示之方法或採用所揭示之組合物。
當提供值的範圍時,應理解除非上下文另外明確指示,否則涵蓋在該範圍之上限與下限之間的各個中間值(至下限之單位的十分之一)及在該指定範圍內之任何其他指定值或中間值。亦涵蓋可獨立地包括於較小範圍中之此等小範圍之上限及下限,在指定範圍內受到任何特定排他性限制。在指定範圍包括限制中之一或兩者時,亦包括排除彼等所包括之限制之任一者或兩者的範圍。
另外的定義可遵循下文。
I.組合物
本發明所揭示之標的物係關於包含/主要由氮穩定劑組分及有機酸酐組分組成之氮穩定組合物。此等氮穩定組合物展現許多有益特性,諸如(但不限於)熱/化學/酶穩定性、存放期增加、揮發性降低、施加速率降低、製備簡易性、操作簡易性、脲酶及硝化抑制之延長/延長作用以及極佳環境及毒理學概況。
氮穩定組合物中存在之各組分(亦即,氮穩定劑組分及有機酸酐組分)之相對量可以變化。舉例而言,在一些實施例中,氮穩定劑組分及有機酸酐組分以在以下範圍內之量存在於氮穩定組合物中:氮穩定劑組分與有機酸酐組分之約1:1,000至約1,000:1;約1:100至約100:1、約1:50至約50:1、約1:25至約25:1、約1:10至約10:1、約1:5至約5:1,或約1:2至2:1,或約1:1莫耳比。在一些實施例中,以氮穩定劑組合物之總重量計,氮穩定組合物中存在之氮穩定劑組分之量的範圍介於約1%至約99%、約1%至約90%、約1%至約80%、約1%至約70%、或約1%至約60%、約1%至約50%、約1%至約40%、約1%至約
30%、約1%至約20%、或約1%至約10%重量(或不超過約50%、約45%、約40%、約35%、約30%、約25%、約20%、約15%,或不超過約10%重量)。
在一些實施例中,以氮穩定劑組合物之總重量計,氮穩定組合物中存在之有機酸酐組分之量的範圍介於約1%至約99%、約1%至約90%、約1%至約80%、約1%至約70%、或約1%至約60%、約1%至約50%、約1%至約40%、約1%至約30%、約1%至約20%,或約1%至約10%重量(或不超過約50%、約45%、約40%、約35%、約30%、約25%、約20%、約15%,或不超過約10%重量)。
在一些實施例中,氮穩定組合物進一步包含一或多種硝化抑制劑及/或一或多種脲酶抑制劑。此等額外硝化及/或脲酶抑制劑可以與氮穩定劑組分中存在之硝化抑制劑及/或脲酶抑制劑相同或不同。
氮穩定劑組分及有機酸酐組分更詳細地論述於下文中。
A.1.氮穩定劑組分
一般而言,本文所揭示之氮穩定劑組分可以為脲酶抑制劑及/或硝化抑制劑。在一些實施例中,脲酶抑制劑及/或硝化抑制劑包含至少一個含胺部分。在一些實施例中,此等含胺部分含有一級胺(亦即-NH2)及/或二級胺(亦即,-NHR;其中R可以為經取代或未經取代之烷基)。
在一些實施例中,氮穩定劑組分為脲酶抑制劑。例示性脲酶抑制劑包括但不限於基於硫代磷酸之脲酶抑制劑,諸如但不限於N-烷基-硫代磷酸三醯胺(例如N-(正丁基)硫代磷酸三醯胺(NBPT)及N-(正丙基)硫代磷酸三醯胺)、N-環烷基-硫代磷酸三醯胺、N-芳基-硫代磷酸三醯胺(例如N-(2-硝基苯基)磷酸三醯胺)及其任何衍生物。在一些實施例中,脲酶抑制劑為NBPT。
在一些實施例中,氮穩定劑組分為脲酶抑制劑之組合。在一些實施例中,一或多種脲酶抑制劑係選自基於硫脲之脲酶抑制劑、基於脲之脲酶
抑制劑、基於磷(二)醯胺之脲酶抑制劑、經取代之半卡腙(例如(2E)-2-[(3-氟苯基)亞甲基]肼-1-甲醯胺及(2E)-2-[(4-硝基苯基)亞甲基]肼-1-甲醯胺)、多酚(例如,沒食子酸甲酯、貝加黃酮(baicalin)、黃芹素(scutellarin)、1,2,3,4,6-戊-O-五倍子醯基-D-葡糖苷、咖啡酸及鞣酸)、羥醛(如柳醛及香草精)、胺基芳族物(如甲氧基苯胺)及其組合。
在一些實施例中,氮穩定劑組分為硝化抑制劑。例示性硝化抑制劑包括但不限於二氰二胺(DCD)及其任何衍生物。在一些實施例中,硝化抑制劑為DCD。在一些實施例中,氮穩定劑組分為硝化抑制劑之組合。在一些實施例中,一或多種硝化抑制劑係選自吡唑(例如3,4-二甲基吡唑及4-氯-3-甲基吡唑)、炔丙基胺、經取代之炔烴(例如2-甲基-3-丁炔-2-醇、3,5-二甲基-1-己炔-3-醇)、經取代之硫脲(例如N-烯丙基硫脲及1-甲脒基-2硫脲)及其組合。
在一些實施例中,氮穩定劑組分為脲酶抑制劑及硝化抑制劑。舉例而言,在一些實施例中,脲酶抑制劑為NBPT且硝化抑制劑為DCD。氮穩定劑組分中存在之脲酶抑制劑及硝化抑制劑的相對量可以變化。舉例而言,在一些實施例中,以氮穩定劑組分之總重量計,脲酶抑制劑之量在約1至約99重量%範圍內且硝化抑制劑之量在約99至約1重量%範圍內。在一些實施例中,以氮穩定劑組分之總重量計,分別地,脲酶抑制劑之量在約10%至約90%、約20%至約80%、約30%至約70%,或40%至約60%重量範圍內,且硝化抑制劑之量在約90%至約10%、約80%至約20%、約70%至約30%、約60%至約40%重量範圍內。在一些實施例中,以氮穩定組合物之總重量計,脲酶抑制劑之量為小於約90%、小於約80%、小於約70%、小於約60%、小於約50%、小於約40%、小於約30%、小於約20%、或小於約10%重量。在一些實施例中,以氮穩定組合物之總重量計,硝化抑制劑之量為小於約90%、小於約80%、小於約70%、小於約60%、小於約50%、小於約40%、小於約30%、小於約20%、或小於約
10%重量。在一些實施例中,脲酶抑制劑及硝化抑制劑以在以下範圍內之量存在於氮穩定組合物中:脲酶抑制劑與硝化抑制劑之約1:100至約100:1;約1:75至約75:1、約1:50至約50:1、約1:25至約25:1、約1:10至約10:1、約1:5至約5:1、或約1:2至2:1,或約1:1莫耳比。
A.2.有機酸酐組分
所揭示之有機酸酐組分選自直鏈有機酸酐單體、環狀有機酸酐單體、直鏈有機酸酐聚合物、環狀有機酸酐聚合物及其組合;其中下文更詳細地描述其中之每一者。
A.2.1.直鏈及環狀有機酸酐單體
其中R1及R2係獨立地選自經取代或未經取代之C1-C8烷基、經取代或未經取代之C2-C8烯基、經取代或未經取代之C3-C8環烷基、經取代或未經取代之芳基,及經取代或未經取代之雜芳基。
在一些實施例中,直鏈有機酸酐單體為飽和的。在一些實施例中,直鏈有機酸酐為不飽和的。在一些實施例中,直鏈有機酸酐單體含有1、2、3、4、5或6個雙鍵。
在一些實施例中,有機酸酐單體為環狀有機酸酐單體。在一些實施例中,環狀有機酸酐組分為單環的。在一些實施例中,環狀有機酸酐為雙環或三環的。
其中------表明可以不飽和(例如表示雙鍵)之上述含酸酐環結構中之任何鍵。
在一些實施例中,環狀有機酸酐單體為飽和的。在一些實施例中,環狀有機酸酐為不飽和的。在一些實施例中,環狀有機酸酐單體含有一個雙鍵。在一些實施例中,環狀有機酸酐單體含有超過一個雙鍵(例如2、3、4或5個雙鍵)。含有一或多個雙鍵之例示性環狀有機酸酐包括但不限於戊烯二酐、3,6-二氫-2,7-氧呯二酮、2,7-氧呯二酮、4,7-二氫-2H-氧-2,8(3H)-二酮,及/或3,4,7,8-四氫-2,9-氧羥二酮。
環狀有機酸酐單體之環大小可以變化。舉例而言,在一些實施例中,環狀有機酸酐單體選自五員、六員、七員、八員、九員、十員、十一員,或十二員環狀有機酸酐單體或其組合。例示性環狀有機酸酐單體包括但不限於戊二酸酐、己二酸酐、2,8-氧雜環辛烷二酮、2,9-氧雜環壬烷二酮、2,10-氧雜環癸烷二酮、癸二酸酐及/或氧雜環癸烷-2,12-二酮。
在一些實施例中,環狀有機酸酐單體為五員環狀有機酸酐單體。在一些實施例中,環狀有機酸酐單體為順丁烯二酸酐。在一些實施例中,環狀有機酸酐單體為丁二酸酐。
在一些實施例中,環狀有機酸酐單體經一或多個取代基取代。在一些實施例中,有機酸酐為雙環或三環。例示性雙環或三環有機酸酐單體包括但不限於六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、雙環庚烯二甲酸酐、氯橋酸酐、鄰苯二甲酸酐、偏苯
三甲酸酐、四氯鄰苯二甲酸酐、苯均四酸二酐、四溴鄰苯二甲酸酐、丁二酸酐、檸康酸酐、順丁烯二酸酐或其組合。
A.2.2.有機酸酐聚合物
如上文所提及,有機酸酐組分亦可以包含有機酸酐聚合物。在一些實施例中,有機酸酐聚合物為兩種不同重複單元之共聚物。在一些實施例中,有機酸酐聚合物為超過兩個不同重複單元之共聚物。在一些實施例中,兩個不同重複單元中之至少一者含有酸酐部分。在一些實施例中,有機酸酐聚合物可以為但不限於無規共聚物、交替共聚物、週期共聚物、統計共聚物或嵌段共聚物。在一些實施例中,有機酸酐聚合物為無規共聚物。
在一些實施例中,有機酸酐聚合物具有高含量之酸酐部分,使其極可溶於水且可生物降解。在一些實施例中,有機酸酐聚合物具有至少75、80、85、90、95或98莫耳%之酸酐部分含量。在一些實施例中,有機酸酐聚合物具有在約50%至約99%、約60%至約98%、約70%至約95%,或約80%至約90莫耳%範圍內的酸酐部分含量。
重複單元衍生自用於合成有機酸酐聚合物之對應單體。在一些實施例中,有機酸酐聚合物含有B型及C型重複單元。此等重複單元及其對應單體更詳細地論述於下文中。
A.3.1.B型重複單元
B型重複單元可以選自衍生自如上文所論述之含有雙鍵之直鏈及/或環狀有機酸酐之經取代或未經取代之單體的重複單元。在一些實施例中,直鏈有機酸酐可以衍生自根據下文所展示之式III之直鏈有機酸酐的單體:
(式III)
其中R1係選自經取代或未經取代之C1-C8烷基、經取代或未經取代之C2-C8烯基、經取代或未經取代之C3-C8環烷基、經取代或未經取代之芳基,及經取代或未經取代之雜芳基;且n為選自0、1、2、3、4、5、6、7、8、9或10之整數。
其中R1及R2獨立地選自-H、-OH、-COOH、-COOR、-OCOH、OCOR、-OR、-CN、-SO2R、-SO3R、-COR、-CONH2、-CONHR、-CONR2、-CHO、NO2、鹵素、-烷基、-環烷基、-芳基、-烷芳基或芳烷基,其中R為經取代或未經取代之烷基;以上環部分上之n展示呈選自1、2、3、4、5、6、7、8、9或10之整數形式的碳原子數;且以上環部分上之m展示呈選自1、2、3、4、5、6、7、8、9或10之整數形式的碳數。
以上式IV中之環狀有機酸酐部分之環大小可以變化。舉例而言,在一些實施例中,環狀有機酸酐單體係選自五員、六員、七員、八員、九員、十員、十一員,或十二員環狀有機酸酐單體或其組合。在一些實施例中,環狀有機酸酐單體為五員環狀有機酸酐部分。
在一些實施例中,B型重複單元衍生自順丁烯二酸酐。在一些實施例中,B型重複單元衍生自伊康酸酐。
在一些實施例中,未經取代或經取代之烷基為C1-C8烷基。
A.3.2.C型重複單元
其中R1、R2、R3及R4獨立地選自-H、-OH、-COOH、-COOR、-OCOH、OCOR、-OR、-CN、-SO2R、-SO3R、-COR、-CONH2、-CONHR、-CONR2、-CHO、NO2、鹵素、-烷基、-環烷基、-芳基、-烷芳基或芳烷基,其中R為經取代或未經取代之烷基。
可使用之單體類別之實例為烯烴,諸如乙烯、丙烯、丁烯-l(丁烯)、異丁烯、戊烯-l、己烯-l、庚烯-l、辛烯-l、2,4,4-三甲基戊烯-l、三甲基乙烯、反式二苯乙烯及亞甲基環己烷;環烯,諸如環戊烯及環己烯;芳烯,諸如苯乙烯、三甲基苯乙烯、a-乙基苯乙烯及其他經取代之苯乙烯衍生物;乙烯醚,諸如甲基乙烯醚、乙基乙烯醚、丙基乙烯醚、異丙基乙烯醚及異丁基乙烯醚;異丙烯醚,諸如甲基異丙烯醚;烯系不飽和羧酸、其酯及腈,諸如丙烯酸甲酯、丙烯酸乙酯、丙烯酸2-乙基己酯、丙烯腈、甲基丙烯酸甲酯及甲基丙烯腈;烯系不飽和二羧酸、其單酯及二酯、腈、酸酐及醯亞胺,諸如順丁烯二酸二甲酯、順丁烯二酸二乙酯、順丁烯二酸二丁酯、順丁烯二酸酐、順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-對氯苯基順丁烯二醯亞胺、反丁烯二酸二甲酯、反丁烯二酸二乙酯、
反丁烯二酸二丁酯、伊康酸酐、伊康酸單丁酯、檸康酸酐、甲基反丁烯二酸酐及亞乙烯基氰;及鹵素取代之烯烴,諸如氯乙烯、偏二氯乙烯、烯丙基氯及甲基烯丙基氯。
在一些實施例中,C型重複單元衍生自乙烯、丙烯、丁烯、異丁烯、苯乙烯、甲基乙烯醚或其組合。
在一些實施例中,經取代或未經取代之烷基為經取代或未經取代之C1-C8烷基。
廣義而言,本文所揭示之有機酸酐聚合物包括由單獨且分別獲自由為了易於參考而命名為B及C部分之部分組成之群的兩個不同部分構成的重複聚合次單元;或者,環狀有機酸酐聚合物可由重複B部分形成。因此,例示性聚合次單元可為BC、CB、BB或B及C部分之任何其他組合;此外,在給定環狀有機酸酐聚合物中,不同聚合次單元可包括不同類型之部分,例如在BC重複聚合單元聚合物中,B部分可在不同單元中不同。
其中R1及R4獨立地選自-H、-OH、-COOH、-COOR、-OCOH、-OCOR、-OR、-CN、-SO2R、-SO3R、-COR、-CONH2、-CONHR、-CONR2、-CHO、NO2、鹵素、-烷基、-環烷基、-芳基、-烷芳基或芳烷基,其中R為經取代或未經取代之C1-C8烷基、經取代或未經取代之C2-C8烯基、經取代或未經取代之芳基、經取代或未經取代之雜芳基;且
R2及R3獨立地選自鍵或經取代或未經取代之C1-C8。
其可以進一步分成以下三個子式:
其中R1、R2、R3及R4獨立地選自-H、-COOH、-COOR、-OCOH、-OCOR、-OR、-CN、-SO2R、-SO3R、-COR、-CONH2、-CONHR、-CONR2、-CHO、NO2、鹵素、-烷基、-環烷基、-芳基、-烷芳基或芳烷基,其中R為經取代或未經取代之C1-C8烷基、經取代或未經取代之C2-C8烯基、經取代或未經取代之芳基、經取代或未經取代之雜芳基。
如可瞭解,所揭示之有機酸酐聚合物可以具有如上文所定義之重複聚合次單元的不同序列(例如,包含B及C次單元之聚合物可包括所有兩種形式之B次單元及所有四種形式之C次單元)。然而,出於成本及易於合成之原因,最適用聚合物包括由B及C部分構成之重複聚合次單元。
其中R1、R2、R3及R4獨立地選自-H、-COOH、-COOR、-OCOH、-OCOR、-OR、-CN、-SO2R、-SO3R、-COR、-CONH2、-CONHR、-CONR2、-CHO、NO2、鹵素、-烷基、-環烷基、-芳基、-烷芳基或芳烷基,其中R為經取代或未經取代之C2-C8烯基、經取代或未經取代之芳基、經取代或未經取代之雜芳基;且n為大於2之整數。
在一些實施例中,此聚合物之其他形式能夠在聚合物中具有廣泛範圍之重複單元濃度。舉例而言,本發明所揭示之主題考慮且包涵具有改變比率之B:C(例如10:90、60:40、50:50及甚至0:100)的聚合物。此等聚合物將由反應混合物中之變化的單體量產生,最終產物最終自該反應混合物產生,且B型及C型重複單元可在聚合物主鏈中以無規次序或以交替模式配置。
在一些實施例中,其中至少約80莫耳%、約85%、約90%或約95%之重複單元為B型重複單元。在一些實施例中,此等重複單元沿聚合物無規安置。
本發明所揭示之標的物之聚合物可具有廣泛多種分子量,例如主要取決於所需最終用途,範圍為約500-5,000,000Da、約1,000-500,000Da或約10,000至約50,000Da。此外,n可以在約1-10,000且更佳約1-5,000範圍內變化。
一般而言,上述聚合物可以藉由自由基聚合製得,由此用重複單元將所選單體轉化為聚合物。該等聚合物可進一步經修改以賦予特定結構及/
或特性。多種技術可以用於產生自由基,諸如添加過氧化物、氫過氧化物、偶氮引發劑、過氧硫酸鹽、過碳酸鹽、過酸、電荷轉移錯合物、照射(例如,電子束、X射線、γ-輻射及其他電離輻射類型)及此等技術之組合。方法及技術之廣泛變化在聚合物化學方法中以用於起始自由基聚合而在本領域中眾所周知。
聚合反應係使用所需單體濃度在相容的溶劑系統(亦即不過度干擾所需聚合之系統)中進行。可以採用多種適合之水性或非水性溶劑系統,諸如酮、醇、酯、醚、芳族溶劑、水及其混合物。單獨的水及較低(C1-C4)酮及醇為尤其較佳的,且此等可視需要與水混合。在一些情況下,聚合反應在實質性排除氧氣之情況下進行,且大多數通常在諸如氮氣或氬氣之惰性氣體下進行。對於用於合成聚合物之設備類型不存在特定的臨界條件,例如,攪拌桶反應器、連續攪拌桶反應器、塞式流動反應器、試管反應器及經串聯配置之前述各者之任何組合均可使用。廣泛範圍之適合的反應配置為聚合領域所熟知的。
一般而言,初始聚合步驟在約0℃至約120℃(或在約30℃至約95℃下持續約0.25小時至約24小時;或約0.25小時至約5小時之時段)之溫度下進行。通常,在連續攪拌下進行反應,且在聚合反應完成後,可以分離聚合物。
B.製備方法
製備如本文所揭示之氮穩定組合物之方法通常包含使氮穩定劑組分與環狀有機酸酐組分接觸。在此情形下,術語「接觸」係指氮穩定劑曝露於有機酸酐組分、與其接觸及/或與其物理混合。兩種組分之接觸通常在兩種組分存在於同一空間(例如反應容器及/或容器)中而不物理上分離時發生。
氮穩定劑及環狀有機酸酐組分之量可以變化。在一些實施例中,在上文所描述之方法的接觸步驟中,存在氮穩定劑與環狀有機酸酐之莫耳
比在約1:10至約10:1、約1:8至約8:1、約1:5至約5:1、約1:3至約3:1、約1:2至約2:1或約1:1範圍內的氮穩定劑及環狀有機酸酐組分之量。
在一些實施例中,上文所描述之方法中之接觸步驟可以不含溶劑進行。在一些實施例中,接觸步驟可以在溶劑中進行。例示性溶劑包括但不限於醇(例如甲醇、乙醇、異丙醇)、醚(例如二乙醚、四氫呋喃)、鹵化溶劑(例如二氯甲烷)、酯(例如乙酸乙酯)、芳族物(例如苯、甲苯)、非極性溶劑(例如乙腈、二甲亞碸)及其類似物。
在一些實施例中,以上接觸步驟可以在室溫(例如約25℃)下進行。在一些實施例中,以上接觸步驟可以在高溫(例如至少30、35、40、45、50、55、60、65、70、75、80、85、90、95或至少100℃)下進行。在一些實施例中,以上接觸步驟可以在低於室溫(例如低於20、10、5、0、-5、-10、-15、-20或低於-30℃)之溫度下進行。在一些實施例中,以上接觸步驟可以在約30℃至約100℃、約40℃至約80℃、約45℃至約75℃,或約50℃至約70℃範圍內之溫度下進行。在一些實施例中,以上接觸步驟可以在低於室溫(例如低於約20、10、5、0、-5、-10、-15、-20或低於約-30℃)之溫度下進行。在一些實施例中,以上接觸步驟可以在約-30℃至約10℃、約-25℃至約5℃、約-15℃至約0℃,或約-10℃至約-5℃範圍內之溫度下進行。
在接觸步驟完成後,可以根據此項技術中已知之方法去除任何殘餘液體(例如溶劑及/或過量氮穩定劑/環有機酸酐組分),且若需要,可以使用此項技術中已知之純化方法(例如高壓液相層析(HPLC)純化、氣相層析(GC)、蒸餾、結晶、層析純化方法(亦即二氧化矽、氧化鋁)及其類似方法)純化剩餘粗物質。
C.氮穩定組合物
如上文所提及,氮穩定組合物可以展現合乎需要之特性,諸如
增加之熱/化學/酶穩定性、增加之存放期、降低之揮發性、降低之施用速率、改良之黏度、製備簡易性、操作簡易性、脲酶及硝化抑制之延長/長期作用,以及極佳環境及毒理學概況,其均通常有助於提高該領域中之效能。
在一些實施例中,氮穩定組合物進一步包含第二硝化抑制劑及/或脲酶抑制劑。第二硝化抑制劑及/或脲酶抑制劑之量可以變化。在一些實施例中,以氮穩定組合物之總重量計,第二硝化抑制劑及/或脲酶抑制劑之量在約1%至約99%、約5%至約90%、約10%至約80%、約10%至約70%、約20%至約60%、或約30%至約50%重量範圍內。在一些實施例中,第二硝化抑制劑及/或脲酶抑制劑與氮穩定劑組分中存在之硝化抑制劑及/或脲酶抑制劑相同。在一些實施例中,相比於氮穩定劑組分中存在之硝化抑制劑及/或脲酶抑制劑,第二硝化抑制劑及/或脲酶抑制劑不同。在一些實施例中,第二硝化抑制劑為氯啶。
在一些實施例中,存在於氮穩定組合物中之氮穩定劑組分及第二硝化抑制劑及/或脲酶抑制劑之量可以在氮穩定劑組分與第二硝化抑制劑及/或脲酶抑制劑之約1:100至約100:1、約1:80至約80:1、約1:50至約50:1、約1:30至約30:1、約1:20至約20:1、約1:10至約10:1、約1:8至約8:1、約1:5至約5:1、約1:3至約3:1、約1:2至2:1,或約1:1的重量比範圍內。
在一些實施例中,相比於不存在有機酸酐之含有氮穩定劑之組合物,本文所揭示之氮穩定組合物在化學/熱/及/或酶上更穩定。在一些實施例中,相比於含有不具有有機酸酐組分之氮穩定劑之組合物,氮穩定組合物之化學穩定性高至少10%、20%、30%、40%、50%、60%、70%、80%、90%或至少95%。在一些實施例中,相比於含有不具有有機酸酐組分之氮穩定劑之組合物,氮穩定組合物之熱穩定性高至少10%、20%、30%、40%、50%、60%、70%、80%、90%或至少95%。在一些實施例中,相比於含有不具有有機酸酐組分之氮穩定劑之組合物,氮穩定組合物之酶穩定性高至少10%、20%、30%、
40%、50%、60%、70%、80%、90%或至少95%。當曝露於化學/熱/酶刺激時,隨在一定時間量之後存在的氮穩定劑之量而變,量測所揭示之組合物之熱/化學/酶穩定性。
在一些實施例中,相比於含有不具有環狀有機酸酐組分之氮穩定劑之組合物,本文所揭示之氮穩定組合物具有較低揮發性。在一些實施例中,相比於含有不具有有機酸酐組分之氮穩定劑之組合物,氮穩定組合物之揮發性低至少10%、20%、30%、40%、50%、60%、70%、80%、90%或至少95%。
在一些實施例中,本文所揭示之氮穩定組合物抑制脲分解。在一些實施例中,氮穩定組合物抑制脲分解至少10%、20%、30%、40%、50%、60%、70%、80%、90%或至少95%。
在一些實施例中,氮穩定組合物提供氮穩定劑組分之穩定及連續釋放。在給定時段內釋放之氮穩定劑組分之量可以變化。熟習此項技術者將意識到如何相應地調變氮穩定劑組分之釋放。舉例而言,熟習此項技術者應瞭解如何藉由選擇適當的有機酸酐組分來調變特定氮穩定劑之釋放特徵以在特定時段內達成氮穩定劑之所需釋放速率。
在一些實施例中,氮穩定劑組分以約1至約100mg/g、約1至約75mg/g、約1至約50mg/g、約1至約40mg/g、約1至約30mg/g、約1至約20mg/g、約1至約10mg/g,或約1至約5mg/g範圍內之穩定濃度自氮穩定組合物釋放。
在一些實施例中,氮穩定劑組分在1-4週、1-3週,或1-2週之時段內自氮穩定組合物釋放。在一些實施例中,氮穩定劑組分在1-30天、1-20天、1-10天之時段內或在至少1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30或
31天之時段內自氮穩定組合物釋放。在一些實施例中,氮穩定劑組分在約1-6個月、1-5個月、1-4個月、1-3個月,或約1-2個月之時段內自氮穩定組合物釋放。
在一些實施例中,氮穩定劑組分在至少10天之時段內以約1至約20mg/g範圍內之濃度自氮穩定組合物釋放。
II.調配物
一般而言,氮穩定劑組合物可以純使用或可以與媒劑(諸如有機溶劑)以及其他成分溶劑化及/或調配以形成適用調配物。在一些實施例中,所描述之氮穩定劑組合物含有相對較少的水至無水。因此,在一些實施例中,以氮穩定劑組合物之總重量計,存在於純氮穩定劑組合物中之水的量小於約10%、約9%、約8%、約7%、約6%、約5%、約4%、約3%、約2%、約1%或小於0.5% w/w。
A.媒劑
在一些實施例中,使純氮穩定劑組合物溶劑化之媒劑包含一或多種有機溶劑。舉例而言,在一些實施例中,媒劑包含/係由/基本上由選自以下之有機溶劑組成:基於乙二醇之溶劑、基於內酯之溶劑、非質子性溶劑、醇溶劑、胺穩定劑及其組合。在一些實施例中,媒劑包含/係由/基本上由選自以下之有機溶劑組成:基於內酯之溶劑、偶極非質子性溶劑、胺穩定劑及其組合。舉例而言,在一些實施例中,媒劑包含/係由/基本上由選自以下之有機溶劑組成:4-丁基-γ-丁內酯、N-甲基-2-吡咯啶酮、二甲亞碸(DMSO)、單乙醇胺及其組合。在一些實施例中,媒劑包含/係由/基本上由選自以下之有機溶劑組成:非質子性溶劑、胺穩定劑及其組合。在一些實施例中,媒劑為DMSO及單乙醇胺。
在一些實施例中,媒劑包含/係由/基本上由非質子性溶劑組成。適合之非質子性溶劑包括例如二氯甲烷、二甲基乙醯胺、二甲基甲醯胺、二甲
亞碸(DMSO)、乙酸乙酯、丙酮、乙腈、六甲基磷醯胺、二甲碸、環丁碸、1,3-二甲基-2-咪唑啶酮、1,3-二甲基-3,4,5,6-四氫-2(1 H)-吡啶酮、乙酸甲酯、乳酸乙酯、N-甲基吡咯啶酮、四氫呋喃及碳酸伸丙酯。在一些實施例中,非質子性溶劑為DMSO。
在一些實施例中,媒劑包含/係由/基本上由胺穩定劑組成。例示性胺穩定劑包括但不限於1,2-二胺基環己烷(DCH)、雙(六亞甲基)三胺(BHT)、單甲醇胺、單乙醇胺、乙胺基乙醇、二甲胺基乙醇、異丙胺基乙醇、二乙醇胺、三乙醇胺、甲胺基乙醇、胺基丙醇、甲胺基丙醇、二甲胺基丙醇、胺基丁醇、二甲胺基丁醇、胺基丁二醇、三羥甲胺基乙烷、二乙胺基丙二醇、1-胺基-環戊烷甲醇及胺基苯甲醇,或雜環,該雜環包含至少一個氮原子作為環成員,及/或在至少一個碳原子上經胺基取代,且在至少一個其他碳原子上經羥烷基或羥基,諸如甲胺基甲基-1,3-二氧戊環取代。在一些實施例中,胺穩定劑為單甲醇胺。
在一些實施例中,媒劑包含/係由/基本上由基於乙二醇之溶劑組成。乙二醇及基於乙二醇之溶劑包括但不限於脂族二羥基(二元)醇。在一個實施例中,基於乙二醇之溶劑包括但不限於聚丙二醇、三甘醇、諸如二丙二醇甲基醚之二醇烷基醚、二甘醇。在另一實施例中,基於乙二醇之溶劑包括但不限於聚乙二醇,諸如聚乙二醇(PEG)及聚丙二醇。乙二醇由通式CnH2n(OH)2表示,其中n為至少2。乙二醇之非限制性實例包括乙二醇(乙二醇)、丙二醇(1,2-丙二醇)、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,9-壬二醇、1,10-癸二醇、1,8-辛二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、2,4-戊二醇、2,5-己二醇、4,5-辛二醇及3,4-己二醇、新戊二醇、、2,2-二乙基-1,3-丙二醇、2-乙基-1,3-己二醇、2-乙基-2-丁基-1,3-丙二醇、異丁烯二醇、2,3-二甲基-1,3-丙二醇、1,3-二苯基-1,3-丙二醇、3-甲基-1,3-丁二醇。基於
聚乙二醇之溶劑包括但不限於聚乙二醇(PEG)200-6000單月桂酸酯及二月桂酯,諸如PEG 600二月桂酸酯、PEG 600單月桂酸酯、PEG 1000二月桂酸酯、PEG 1000單月桂酸酯、PEG 1540二月桂酸酯及PEG 1540單月桂酸酯;聚乙二醇200-6000單油酸酯及二油酸酯,諸如PEG 400單油酸酯、PEG 600二油酸酯、PEG 600單油酸酯、PEG 1000單油酸酯、PEG 1540二油酸酯、PEG 1540單油酸酯及聚乙二醇200-6000單硬脂酸酯及二硬脂酸酯,諸如PEG 400二硬脂酸酯、PEG 400單硬脂酸酯、PEG 600二硬脂酸酯、PEG 600單硬脂酸酯、PEG 1000二硬脂酸酯、PEG 1000單硬脂酸酯、PEG 1540二硬脂酸酯、PEG 1540單硬脂酸酯及PEG 3000單硬脂酸酯。
在一些實施例中,媒劑包含/係由/基本上由基於內酯之溶劑組成。內酯為不同環大小之環狀羧酸酯。在一些實施例中,基於內酯之溶劑係選自α-乙醯內酯、β-丙內酯、γ-丁內酯及δ-戊內酯。在一些實施例中,α-乙醯內酯、β-丙內酯、γ-丁內酯及/或δ-戊內酯視情況經例如烷基或鹵素取代。例示性基於內酯之溶劑包括但不限於4-丁基-γ-丁內酯、黏溴酸、黏氯酸、β-丁內酯、γ-丁內酯、3-羥基-γ-丁內酯、α-亞甲基-γ-丁內酯及γ-戊內酯。
在一些實施例中,媒劑包含/係由/基本上由醇溶劑組成。醇溶劑為任何含有羥基(-OH)之有機溶劑。例示性醇溶劑包括但不限於乙醇、甲醇、第三戊醇、2-甲基-1-丁醇、2-甲基-1-戊醇、3-甲基-2-丁醇、糠醇、2-丁醇、正丁醇、異丁醇、異丙醇、2-戊醇、1-丙醇及其組合。
在一些實施例中,媒劑相對不含水。在一些實施例中,以媒劑之總重量計,媒劑(例如有機溶劑)含有小於約10% w/w、約9% w/w、約8% w/w、約7% w/w、約6% w/w、約5% w/w、約4% w/w、約3% w/w、約2% w/w、約1% w/w、約0.9% w/w、約0.8% w/w、約0.7% w/w、約0.6% w/w、約0.5% w/w、約0.4% w/w、約0.3% w/w,或低於約0.1% w/w之水。
B.調配物
本文所揭示之媒劑可以用於含有上述氮穩定組合物及/或其組分之調配物中以得到展現許多有利特性之調配物,該等特性諸如但不限於熱及/或化學調配穩定性、增加之調配物存放期、降低之調配物揮發性、降低之施用速率、改良調配物黏度、不存在任何強烈難聞臭味或氣味、調配物製備簡易性、調配物操作簡易性、脲酶及硝化抑制之延長/長期作用,以及極佳環境及毒理學概況。
在一些實施例中,調配物包含所揭示之氮穩定組合物及如上文所描述之媒劑。存在於調配物中之氮穩定組合物之量可以變化。舉例而言,在一些實施例中,以調配物之總重量計,存在於調配物中之氮穩定組合物之量在約5%至約50%、約10%至約45%、約15%至約40%、約20%至約35%,或約25%至約30% w/w範圍內。在一些實施例中,以調配物之總重量計,存在於調配物中之氮穩定組合物之量在約1%至約75%、約10%至約65%、約20%至約65%、約30%至約65%,或約40%至約65% w/w範圍內。在一些實施例中,以調配物之總重量計,存在於調配物中之氮穩定組合物之量在約1%至約40%、約10%至約35%、約15%至約35%、約20%至約35%、約25%至約35%、約27%至約35%,或約30%至約35% w/w範圍內。在一些實施例中,以調配物之總重量計,存在於調配物中之氮穩定組合物之量在約15%至約30%、約15%至約28%、約15%至約25%,或約15%至約23% w/w範圍內。在一些實施例中,以調配物之總重量計,存在於調配物中之氮穩定組合物之量在約25%至約40%、約25%至約35%、約22%至約28%,或約22%至約33% w/w範圍內。
在一些實施例中,氮穩定劑組分(其為氮穩定組合物之一部分)之量可以變化。在一些實施例中,以調配物之總重量計,氮穩定劑組分存在於調配物中之量在約1%至約50%、約5%至約50%、約5%至約40%、約10%至
約40%、約10%至約30%,或約10%至約25% w/w範圍內。在一些實施例中,存在於調配物中之氮穩定劑組分之量在約5%至約30%、約5%至約25%、約5%至約20%、約5%至約15%,或約5%至約10%範圍內。在一些實施例中,存在於調配物中之氮穩定劑組分之量在約15%至約30%、約15%至約25%,或約15%至約20%範圍內。在一些實施例中,氮穩定劑組分為脲酶抑制劑。在一些實施例中,氮穩定劑組分為硝化抑制劑。在一些實施例中,氮穩定劑組分為硝化抑制劑及脲酶抑制劑。
在一些實施例中,氮穩定組分包含脲酶抑制劑。存在於調配物中之脲酶抑制劑(其為氮穩定劑組分之一部分)之量可以變化。舉例而言,在一些實施例中,以調配物之總重量計,存在於調配物中之脲酶抑制劑之量在約5%至約50%、5%至約25%、5%至約20%,或5%至約15% w/w範圍內。在一些實施例中,以調配物之總重量計,存在於調配物中之脲酶抑制劑之量在約5%至約30%、約5%至約25%、約5%至約20%、約5%至約15%、約5%至約10%,或約5%至約8.5% w/w範圍內。在一些實施例中,存在於調配物中之脲酶抑制劑之量在約15%至約25%、約15%至約20%,或約10%至約20%、約10%至約15%、約12.5%至約15%,或約7.5%至約20%、約8.5%至約20%、約8.5%至約15%,或約8.5%至約12.5%範圍內。在一些實施例中,脲酶抑制劑為NBPT。
在一些實施例中,氮穩定劑組分包含硝化抑制劑。存在於調配物中之硝化抑制劑之量可以變化。舉例而言,在一些實施例中,以調配物之總重量計,存在於調配物中之硝化抑制劑之量在約1%至約30%、約5%至約25%、約5%至約20%、5%至約10%,或10%至約20% w/w範圍內。在一些實施例中,以調配物之總重量計,存在於調配物中之硝化抑制劑之量在約5%至約30%、約5%至約25%、約5%至約20%、約5%至約15%、約5%至約10%,或約5%至約7.5% w/w範圍內。在一些實施例中,存在於調配物中之脲酶抑制劑之量在約
15%至約25%、約15%至約20%,或約10%至約25%、約10%至約20%、約10%至約15%,或約7.5%至約25%,或約7.5%至約15%範圍內。在一些實施例中,硝化抑制劑為DCD。
在一些實施例中,以調配物之總重量計,存在於調配物中之有機酸酐組分(其為氮穩定組合物之一部分)之量在約1%至約20%、約1%至約15%,或約1%至約10% w/w範圍內。在一些實施例中,存在於調配物中之有機酸酐組分之量在約5%至約15%、約5%至約10%,或約5%至約8%範圍內。在一些實施例中,有機酸酐組分為如本文所揭示之聚合物。
在一些實施例中,媒劑可以用於溶劑化及/或調配氮穩定組合物之一或多個組分。舉例而言,在一些實施例中,調配物包含如本文所揭示之氮穩定劑組合物及媒劑。在一些實施例中,調配物包含如本文所揭示之脲酶抑制劑及媒劑。在一些實施例中,脲酶抑制劑為NBPT。
在一些實施例中,調配物包含如本文所揭示之硝化抑制劑及媒劑。在一些實施例中,硝化抑制劑為DCD。
在一些實施例中,調配物包含如本文所揭示之硝化抑制劑、脲酶抑制劑及媒劑。在一些實施例中,硝化抑制劑為DCD且脲酶抑制劑為NBPT。
在一些實施例中,調配物包含如本文所揭示之有機酸酐組分及媒劑。在一些實施例中,有機酸酐組分為如本文所揭示之聚合物。
用以溶劑化及/或調配上文所提及之組合物及/或組分之媒劑包含非質子性溶劑及胺穩定劑。熟習此項技術者應瞭解,存在於調配物中之非質子性溶劑及胺穩定劑之量可變化。舉例而言,在一些實施例中,以調配物之總重量計,非質子性溶劑之量在約1%至約80%、約10%至約80%、約20%至約80%、約40%至約80%、50%至約75%、約55%至約75%,或約60%至約75% w/w
範圍內。在一些實施例中,以調配物之總重量計,存在於調配物中之非質子性溶劑之量在約10%至約75%、約10%至約60%、約10%至約50%、約10%至約45%,或約20%至約45% w/w範圍內。
在一些實施例中,以調配物之總重量計,非質子性溶劑之量小於約80%、約75%、約70%、約65%、約60%、約55%、約50%、約45%、約40%、約30%或約20% w/w。在一些實施例中,以調配物之總重量計,非質子性溶劑之量大於約5%、約10%、約15%、約20%、約25%、約30%、約35%、約40%、約45%、約50%、約55%、約60%、約65%、約70%、約75% w/w。在一些實施例中,非質子性溶劑為DMSO。在一些實施例中,以調配物之總重量計,胺穩定劑之量在約1%至約15%、約5%至約10%、約3%至約8%,或約8%至約12% w/w範圍內。在一些實施例中,以調配物之總重量計,胺穩定劑之量小於約15%、約14%、約13%、約12%、約11%、約10%、約9%、約8%、約7%、約6%、約5%、約4%、約3%、約2%或約1% w/w。在一些實施例中,以調配物之總重量計,胺穩定劑之量大於約1%、約2%、約3%、約4%、約5%、約6%、約7%、約8%、約9%、約10%或約12% w/w。在一些實施例中,胺穩定劑為單甲醇胺。
因此,在一些實施例中,如本文所揭示之調配物包含氮穩定劑組合物及非質子性溶劑及胺穩定劑。
在一些實施例中,如本文所揭示之調配物包含氮穩定劑組分;非質子性溶劑;及胺穩定劑。
在另一實施例中,如本文所揭示之調配物包含有機酸酐組分;非質子性溶劑;及胺穩定劑。
如上述任何實施例中之調配物,其中氮穩定包含氮穩定劑組分;及有機酸酐組分。
如上述任何實施例中之調配物,其中氮穩定劑組分為脲酶抑制劑及/或硝化抑制劑。
在一些實施例中,如本文所揭示之調配物包含:包含氮穩定劑組分之氮穩定組合物;及有機酸酐組分,其中氮穩定劑組分為脲酶抑制劑及/或硝化抑制劑;非質子性溶劑;及胺穩定劑。
如上述任何實施例中之調配物,其中氮穩定劑組分為N-(正丁基)硫代磷酸三醯胺(NBPT)及/或二氰胺(DCD)。
如上述任何實施例中之調配物,其中有機酸酐組分為有機酸酐聚合物。
如上述任何實施例中之調配物,其中有機酸酐聚合物為含有至少兩種不同重複單元,包括B型重複單元中之一者及C型重複單元中之一者的共聚物。
如上述任何實施例中之調配物,其中共聚物為無規共聚物。
如上述任何實施例中之調配物,其中B型重複單元衍生自順丁烯二酸酐、伊康酸酐或其組合之(未)經取代之單體。
如上述任何實施例中之調配物,其中B型重複單元衍生自順丁烯二酸酐之(未)經取代之單體。
如上述任何實施例中之調配物,其中至少約50莫耳%之有機酸酐聚合物之重複單元為B型重複單元。
如上述任何實施例中之調配物,其中有機酸酐聚合物含有衍生自(未)經取代之烯烴之C型重複單元。
如上述任何實施例中之調配物,其中烯烴係選自乙烯、丙烯、丁烯、異丁烯、苯乙烯、甲基乙烯基醚及其組合。
其中R1、R2、R3及R4獨立地選自-H、-COOH、-COOR、-OCOH、-OCOR、-OR、-CN、-SO2R、-SO3R、-COR、-CONH2、-CONHR、-CONR2、-CHO、NO2、鹵素、-烷基、-環烷基、-芳基、-烷芳基或芳烷基,其中R為未經取代之C1-C8烷基、未經取代之C2-C8烯基、未經取代之芳基、未經取代之雜芳基;且n為大於2之整數。
如上述任何實施例中之調配物,其中非質子性溶劑係選自二氯甲烷、二甲基乙醯胺、二甲基甲醯胺、二甲亞碸(DMSO)、乙酸乙酯、丙酮、乙腈、六甲基磷醯胺、二甲碸、環丁碸、1,3-二甲基-2-咪唑啶酮、1,3-二甲基-3,4,5,6-四氫-2(1 H)-嘧啶酮、乙酸甲酯、乳酸乙酯、N-甲基吡咯啶酮、四氫呋喃及碳酸伸丙酯。
如上述任何實施例中之調配物,其中非質子性溶劑為二甲亞碸(DMSO)。
如上述任何實施例中之調配物,其中胺穩定劑係選自1,2-二胺基環己烷(DCH)、雙(六亞甲基)三胺(BHT)、單乙醇胺、乙胺基乙醇、二甲胺基乙醇、異丙基胺基乙醇、二乙醇胺、三乙醇胺、甲胺基乙醇、胺基丙醇、甲胺基丙醇、二甲胺基丙醇、胺基丁醇、二甲胺基丁醇、胺基丁二醇、三羥甲胺基乙烷、二乙胺基丙二醇、1-胺基-環戊烷甲醇及胺基苯甲醇。
如上述任何實施例中之調配物,其中胺穩定劑為單乙醇胺。
如上述任何實施例中,將包含如本文所揭示之DCD、NBPT及聚合物之調配物調配於DMSO及單甲醇胺中。
如上述任何實施例中之調配物,其中以穩定調配物之總重量計,氮穩定組合物係以約5%至約50% w/w之量存在。
如上述任何實施例中之調配物,其中以穩定調配物之總重量計,非質子性溶劑係以約50%至約75% w/w之量存在。
如上述任何實施例中之調配物,其中以穩定調配物之總重量計,胺穩定劑係以約3%至約8% w/w之量存在。
如上述任何實施例中之調配物,其中以穩定調配物之總重量計,氮穩定劑組分係以約5%至約50% w/w之量存在。
如上述任何實施例中之調配物,其中氮穩定劑組分包含以穩定調配物之總重量計,以約5%至約20% w/w之量存在的脲酶抑制劑,及以穩定調配物之總重量計,以約5%至約20% w/w之量存在的硝化抑制劑。
如上述任何實施例中之調配物,其中氮穩定劑組分包含以約5%至約20% w/w之量存在的脲酶抑制劑及以約5%至約20% w/w之量存在的硝化抑制劑,及以約1%至約10%之量存在的如本文所揭示之聚合物;以及媒劑,其包含以約45%至約75%之量存在的非質子性溶劑及以約3%至約8% w/w之量存在的胺穩定劑,其中所有重量均以穩定調配物之總重量計。在一些實施例中,相比於含有不存在有機酸酐組分之氮穩定組合物之調配物,本文所揭示之調配物為化學及/或熱更穩定的。在一些實施例中,相比於含有不具有有機酸酐組分之氮穩定組合物之調配物,調配物之化學穩定性高至少10%、20%、30%、40%、50%、60%、70%、80%、90%或至少95%。在一些實施例中,相比於含有不具有有機酸酐組分之氮穩定組合物之調配物,調配物之熱穩定性高至少10%、20%、30%、40%、50%、60%、70%、80%、90%或至少95%。當曝露於化學
及/或熱及/或刺激時,隨在一定時間量之後存在的氮穩定劑之量而變,量測所揭示之組合物之熱及/或化學穩定性。
在一些實施例中,相比於含有不具有有機酸酐組分之氮穩定組合物之調配物,本文所揭示之調配物具有較低揮發性。在一些實施例中,相比於含有不具有有機酸酐組分之氮穩定組合物之調配物,調配物之揮發性低至少10%、20%、30%、40%、50%、60%、70%、80%、90%或至少95%。
在一些實施例中,相比於含有不具有有機酸酐組分之氮穩定組合物之調配物,本文所揭示之調配物展現改良之黏度。在一些實施例中,當在室溫(25.5℃)下量測時,所揭示之調配物之黏度在約50至約1,740cp範圍內。在一些實施例中,當在約2℃下量測時,所揭示之調配物之黏度在約200至約9,500cp範圍內。
在一些實施例中,本文所揭示之調配物不包含強烈難聞的氣味及/或臭味。難聞的臭味或氣味之特徵可為具有含硫臭味或氣味。出人意料地,儘管如本文所揭示之調配物含有DMSO,但其並不展現任何難聞的氣味及/或臭味。缺乏難聞的氣味及/或異味使調配物與其他調配物相比對使用者更友好,此可展現難聞的氣味及/或臭味。可以使用此項技術中已知之方法偵測及/或鑑別源自調配物之任何難聞的氣味及/或臭味。例示性方法包括但不限於蒸氣壓量測及/或氣相層析以偵測及/或鑑別已知展現難聞的氣味及/或臭味之有機化合物。
舉例而言,調配物之蒸氣壓降低與特定調配物之難聞的氣味及/或臭味減少相關。因此,在一些實施例中,如本文所揭示之調配物展現相比於市售調配物(例如Eco Argo's NEONTM家族產品),展現出蒸氣壓降低至少約5%、約10%、約15%、約20%、約25%、約30%、約35%、約40%、約45%、約50%、約55%。
亦可以使用用於量測及鑑別難聞氣味及/或臭味之裝置。例示性
裝置包括氣味計、電子鼻,其可以以電子方式「聞嗅」難聞臭味及/或氣味(例如參見美國專利10,603,858,其特此以全文引用之方式併入)及其類似者。舉例而言,使用諸如電子鼻之裝置偵測難聞臭味及/或氣味之例示性方法可包含:將如本文所揭示之調配物置放在封閉容器中;密封容器一定時段;重新打開容器;及藉由電子鼻以電子方式聞嗅調配物,其中進行藉由電子鼻以電子方式聞嗅之步驟以便判定調配物是否具有含硫氣味。在一些實施例中,容器在密封步驟期間可曝露於高溫。在一些實施例中,以電子方式聞嗅包含藉由複數個感測器將空浮製品抽取至感測空浮粒子之樣品室中;處理自複數個感測器獲得之資料以確定空浮粒子中之任一者是否為調配物之空浮粒子;且表明存在之調配物之空浮粒子的存在及/或數量。
因此,在一些實施例中,如本文所揭示之調配物展現相比於市售調配物(例如Eco Argo's NEONTM家族產品)之反應速率,反應速率降低至少約5%、10%、15%、20%、25%、30%、35%、40%、45%、50%。
III.農業組合物
所描述之氮穩定組合物及/或調配物中之任一者可以與選自由以下組成之群的一或多種其他成分組合:肥料、農業活性化合物、種子、農藥、除草劑、殺昆蟲劑、殺真菌劑、殺蟎劑及其類似物。
在一些實施例中,所描述之氮穩定組合物及/或調配物可與肥料產品混合,作為表面塗層施用於肥料產品,或另外與肥料產品充分混合。在一些實施例中,在此類組合肥料/氮穩定組合物產品中,肥料呈平均直徑為約粉末尺寸(小於約0.001cm)至約10mm、更佳約0.1mm至約5mm,且再更佳約0.15mm至約3mm的粒子形式。氮穩定組合物及/或可以以約0.001g至約20g/100g肥料、約0.01至7g/100g肥料、約0.08g至約5g/100g肥料,或約0.09g至約2g/100g肥料之位準存在於此等組合產品中。在組合肥料/氮穩定組合物產品之情況
下,組合產品可以以使得施用的氮穩定組合物及/或調配物之量為每英畝土壤約10-150g、每英畝約30-125g,或每英畝土壤約40-120g的位準施用。由使用者酌情處理,組合產品可以同樣地以液體分散液或乾燥粒狀產品之形式施用。當氮穩定組合物及/或調配物用作塗料時,氮穩定組合物及/或調配物可以包含約0.005重量%與約15重量%之間的經塗佈肥料產品、約0.01重量%與約10重量%之間的經塗佈肥料產品、約0.05重量%與約2重量%之間的經塗佈肥料產品或約0.5重量%與約1重量%之間的經塗佈肥料產品。
A.肥料
在一些實施例中,農業產品為肥料。肥料可以為固體肥料,諸如但不限於粒狀及/或球粒狀肥料,且氮穩定組合物及/或調配物可以作為液體分散液施用至肥料或可以與其互混。肥料亦可以呈半固體形式(例如糞肥),其中氮穩定組合物及/或調配物亦可以作為液體分散液施用至肥料或可以與其互混。肥料亦可以呈液體形式,且氮穩定組合物及/或調配物可以與液體肥料混合。
在一些實施例中,肥料為或含有脲及/或氨,包括無水氨肥料。在液體肥料(諸如UAN)之情況下,氮穩定組合物及/或調配物通常以適當量與肥料液體混合。在含有脲之液體肥料中,脲通常以約1-12莫耳/L,更佳約2-10莫耳/公升之含量存在。另一替代方案將為在製造此等產品期間用氮穩定組合物浸漬脲或含有脲之肥料。雖然組合物應含有呈一些形式之脲,但其他類型之肥料可用於農業組合物中。
此等額外次級肥料可以選自由以下組成之群:種肥(starter fertilizer)、基於磷酸鹽之肥料、含氮肥料、含磷肥料、含鉀肥料、含鈣肥料、含鎂肥料、含硼肥料、含氯肥料、含鋅肥料、含錳肥料,及/或含銅肥料。在一些實施例中,額外肥料包含植物可用之氮、磷、鉀、硫、鈣、鎂或微量養分。
在一些實施例中,肥料為固體、粒狀、流體懸浮液、氣體或固溶肥料。在一些實施例中,肥料包含微量養分。微量養分為植物少量需要之必需要素。在一些實施例中,肥料包含選自由以下組成之群的金屬離子:Fe、Mn、Mg、Zn、Cu、Ni、Co、Mo、V及Ca。在一些實施例中,肥料包含石膏、硫鎂礬族成員、鉀產品、硫酸鉀鎂、單質硫或硫酸鉀鎂。此等肥料可為粒狀、液體、氣體或混合物(例如固體肥料顆粒於液態物質中之懸浮液)。在一些實施例中,額外肥料為NPK肥料。
一般而言,此等次級肥料之量將小於脲部分之量。此等含有本文所揭示之氮穩定劑組合物的雙重肥料組合物可精確地與施用於田地及/或作物的對應脲肥料產品相同的方式及相同的量使用。在固體或半固體之情況下,在種植之前、期間或之後,產品可藉由播施、深層或次表面置放、局部置放、接觸、帶狀、丘陵及列狀置放以相同數量施用。液體組合物將通常藉由用切入(knife-in)或其他習知方法將液體併入土壤中來施用。
當所描述之氮穩定劑組合物或其調配物與施用一或多種肥料一起施用時,氮穩定劑組合物可以在施用肥料之前、在其之後或與其同時施用。
如上所述,含有如本文所揭示之氮穩定劑組合物及/或調配物的肥料組合物可以以將有益於所關注作物的任何方式施用。在一些實施例中,在播種或移植所需農作物植物之前向生長介質或在整個生長介質中施用此等組合物。在一些實施例中,組合物可以施用於生長植物之根部區。
B.種子
在一些實施例中,農業種子包覆有所描述之氮穩定劑組合物及/或調配物中之一或多者。以所包覆之種子產品之總重量計,氮穩定劑組合物及/或調配物可以以約0.001重量%-10%重量%、約0.004重量%-2重量%、約0.01重量%-約1重量%,或約0.1重量%-約1重量%(或不超過約10重量%、約9重量%、
約8重量%、約7重量%、約6重量%、約5重量%、約4重量%、約3重量%、約2重量%、約1重量%、約0.5重量%、約0.1重量%、約0.01重量%、或不超過0.001重量%)之含量存在於種子產品中。種子可以為(但不限於)小麥、大麥、燕麥、黑小麥、粗麥、稻穀、玉米、大豆、棉或油菜。
C.其他
在一些實施例中,殺蟲劑、除草劑、殺昆蟲劑、殺真菌劑及/或殺蟎劑與一或多種所描述之氮穩定劑組合物及/或調配物組合。如本文所使用,「農藥」係指具有農藥活性之任何試藥劑(例如除草劑、殺昆蟲劑、殺真菌劑)且較佳係選自由殺昆蟲劑、除草劑及其混合物組成之群,但通常不包括據說具有植物施肥效應之物質,例如硼酸鈉及諸如氧化鋅、硫酸鋅及氯化鋅之鋅化合物。關於農藥之非限制性清單,參見「Farm Chemicals Handbook 2000,2004」(Meister Publishing Co,Willoughby,OH),其特此以全文引用之方式併入。
例示性除草劑包括(但不限於)乙草胺(acetochlor)、拉草(alachlor)、氯胺吡啶酸(aminopyralid)、草脫凈(atrazine)、解草酮(benoxacor)、溴苯腈(bromoxynil)、唑草酮(carfentrazone)、氯磺隆(chlorsulfuron)、炔草酸(clodinafop)、畢克草(clopyralid)、汰克草麥草畏(dicamba)、禾草靈(diclofop-methyl)、汰草滅(dimethenamid)、芬殺草(fenoxaprop)、氟酮磺隆(flucarbazone)、氟噻草胺(flufenacet)、唑嘧磺草胺(flumetsulam)、氟胺草酯(flumiclorac)、氟氯比(fluroxypyr)、固殺草(glufosinate-ammonium)、嘉磷塞(glyphosate)、合速隆(halosulfuron-methyl)、咪草酸(imazamethabenz)、甲氧咪草菸(imazamox)、依滅草(imazapyr)、滅草喹(imazaquin)、咪唑乙菸酸(imazethapyr)、異唑草酮(isoxaflutole)、快克草(quinclorac)、MCPA、MCP胺、MCP酯、右滅達樂
(mefenoxam)、甲基磺草酮(mesotrione)、莫多草(metolachlor)、左旋莫多草(s-metolachlor)、滅畢淨(metribuzin)、甲磺隆(metsulfuron methyl)、菸嘧磺隆(nicosulfuron)、巴拉刈(paraquat)、施得圃(pendimethalin)、畢克爛(picloram)、氟嘧磺隆(primisulfuron)、丙苯磺隆(propoxycarbazone)、氟磺隆(prosulfuron)、霸草靈(pyraflufen ethyl)、碸嘧磺隆(rimsulfuron)、草滅淨(simazine)、磺醯磺隆(sulfosulfuron)、噻吩磺隆(thifensulfuron)、苯吡唑草酮(topramezone)、三甲苯草酮(tralkoxydim)、野麥畏(triallate)、醚苯磺隆(triasulfuron)、苯磺隆(tribenuron)、三氯比(triclopyr)、三福林(trifluralin)、2,4-D、2,4-D胺、2,4-D酯及其類似者。
例示性殺昆蟲劑包括(但不限於)1,2二氯丙烷、1,3二氯丙烯、阿巴汀(abamectin)、歐殺松(acephate)、亞醌蟎(acequinocyl)、亞滅培(acetamiprid)、家蠅磷(acethion)、乙醯蟲腈(acetoprole)、阿納寧(acrinathrin)、丙烯腈、棉靈威(alanycarb)、得滅克(aldicarb)、涕滅碸威(aldoxycarb)、艾氏劑(aldrin)、亞列寧(allethrin)、阿洛氨菌素(allosamidin)、除害威(allyxycarb)、α賽滅寧(alpha cypermethrin)、α蛻皮激素(alpha ecdysone)、賽果(amidithion)、安米氟美(amidoflumet)、滅害威(aminocarb)、胺吸磷(amiton)、三亞蟎(amitraz)、毒藜鹼(anabasine)、氧化砷、乙基殺撲磷(athidathion)、印楝素(azadirachtin)、亞滅松(azamethiphos)、乙基穀硫磷(azinphos ethyl)、甲基穀硫磷(azinphos methyl)、偶氮苯、亞環錫(azocyclotin)、偶氮磷、六氟矽酸鋇、熏菊酯(barthrin)、苯氯噻(benclothiaz)、惡蟲威(bendiocarb)、免扶克(benfuracarb)、苯惡磷(benoxafos)、免速達(bensultap)、西脫蟎(benzoximate)、苯甲酸苯甲酯、β賽扶寧(beta cyfluthrin)、β賽滅寧(beta cypermethrin)、畢芬載(bifenazate)、畢芬寧(bifenthrin)、百蟎克
(binapacryl)、百亞列寧(bioallethrin)、戊環苄呋菊酯(bioethanomethrin)、生物氯菊酯(biopermethrin)、雙三氟蟲脲(bistrifluron)、硼砂、硼酸、溴苯烯磷(bromfenvinfos)、溴DDT、溴烯殺(bromocyclen)、溴磷松(bromophos)、乙基溴磷松、溴蟎酯(bromopropylate)、合殺威(bufencarb)、布芬淨(buprofezin)、畜蟲威(butacarb)、特嘧硫磷(butathiofos)、丁酮威(butocarboxim)、丁酯磷(butonate)、丁酮碸威(butoxycarboxim)、硫線磷(cadusafos)、砷酸鈣、聚硫化鈣、毒殺芬(camphechlor)、氯滅殺威(carbanolate)、加保利(carbaryl)、加保扶(carbofuran)、二硫化碳、四氯化碳、三硫磷、丁基加保扶(carbosulfan)、培丹(cartap)、蟎離丹(chinomethionat)、剋安勃(chlorantraniliprole)、氯殺蟎(chlorbenside)、冰片丹(chlorbicyclen)、氯丹(chlordane)、十氯酮(chlordecone)、殺蟲脒(chlordimeform)、氯氧磷(chlorethoxyfos)、克凡派(chlorfenapyr)、殺蟎醇(chlorfenethol)、殺蟎酯(chlorfenson)、敵蟎特(chlorfensulphide)、克芬松(chlorfenvinphos)、克福隆(chlorfluazuron)、氯甲磷(chlormephos)、乙酯殺蟎醇(chlorobenzilate)、氯仿(chloroform)、滅蟎眯(chloromebuform)、滅蟲脲(chloromethiuron)、氯化苦(chloropicrin)、丙酯殺蟎醇(chloropropylate)、氯腈肟磷(chlorphoxim)、氯吡唑磷(chlorprazophos)、陶斯松(chlorpyrifos)、甲基陶斯松、蟲蟎磷(chlorthiophos)、可芬諾(chromafenozide)、瓜菊酯I(cinerin I)、瓜菊酯II、順式苄呋菊酯(cismethrin)、地蟲威(cloethocarb)、克芬蟎(clofentezine)、氯氰碘柳胺(closantel)、可尼丁(clothianidin)、乙醯亞砷酸銅、砷酸銅、環烷酸銅、油酸銅、蠅毒磷(coumaphos)、畜蟲磷(coumithoate)、克羅米通(crotamiton)、巴毒磷(crotoxyphos)、克魯恩特侖A&B(cruentaren A & B)、育畜磷(crufomate)、冰晶石(cryolite)、施力松(cyanofenphos)、氰乃松
(cyanophos)、果蟲磷(cyanthoate)、環蟲菊酯(cyclethrin)、乙氰菊脂(cycloprothrin)、唑蟎氰(cyenopyrafen)、丁氟蟎酯(cyflumetofen)、賽扶寧(cyfluthrin)、賽洛寧(cyhalothrin)、錫蟎丹(cyhexatin)、賽滅寧(cypermethrin)、賽酚寧(cyphenothrin)、賽滅淨(cyromazine)、畜蜱磷(cythioate)、d-檸檬烯(d-limonene)、邁隆(dazomet)、DBCP、DCIP、DDT、一甲呋喃丹(decarbofuran)、第滅寧(deltamethrin)、田樂磷(demephion)、田樂磷O(demephion O)、田樂磷S(demephion S)、內吸磷(demeton)、甲基內吸磷(demeton methyl)、內吸磷O(demeton O)、甲基內吸磷O(demeton O methyl)、內吸磷S(demeton S)、甲基內吸磷S(demeton S methyl)、甲磺酸內吸磷S(demeton S methylsulphon)、汰芬諾克(diafenthiuron)、氯亞胺硫磷(dialifos)、二胺磷(diamidafos)、大利松(diazinon)、異氯硫磷(dicapthon)、除線磷(dichlofenthion)、益發靈(dichlofluanid)、二氯松(dichlorvos)、大克蟎(dicofol)、敵來死(dicresyl)、雙特松(dicrotophos)、地昔尼爾(dicyclanil)、地特靈(dieldrin)、除蟎靈(dienochlor)、氟蟎(diflovidazin)、二福隆(diflubenzuron)、雙羥丙茶鹼(dilor)、四氟甲醚菊酯(dimefluthrin)、甲氟磷(dimefox)、地麥威(dimetan)、大滅松(dimethoate)、苄菌酯(dimethrin)、甲基毒蟲畏(dimethylvinphos)、敵蠅威(dimetilan)、消蟎酚(dinex)、敵蟎通(dinobuton)、白粉克(dinocap)、白粉克4、白粉克6、鄰敵蟎消(dinocton)、硝戊酯(dinopenton)、丙硝酚(dinoprop)、戊硝酚(dinosam)、硝辛酯(dinosulfon)、達特南(dinotefuran)、硝丁酯(dinoterbon)、苯蟲醚(diofenolan)、蔬果磷(dioxabenzofos)、二氧威(dioxacarb)、敵殺磷(dioxathion)、二苯基碸(diphenyl sulfone)、二硫龍(disulfiram)、二硫松(disulfoton)、噻喃磷(dithicrofos)、DNOC、苯氧炔蟎(dofenapyn)、多拉克
汀(doramectin)、脫皮甾酮(ecdysterone)、因滅汀(emamectin)、EMPC、烯炔菊酯(empenthrin)、安殺番(endosulfan)、因毒磷(endothion)、異地特靈(endrin)、EPN、保幼醚(epofenonane)、依普菌素(eprinomectin)、益化利(esfenvalerate)、偏磷酸(etaphos)、乙硫苯威(ethiofencarb)、愛殺松(ethion)、乙蟲腈(ethiprole)、甲基益果(ethoate methyl)、普伏松(ethoprophos)、乙滴滴(ethyl DDD)、二溴乙烷、二氯化乙烯、環氧乙烷、依芬寧(etofenprox)、依殺蟎(etoxazole)、乙嘧硫磷(etrimfos)、EXD、伐滅磷(famphur)、芬滅松(fenamiphos)、抗蟎唑(fenazaflor)、芬殺蟎(fenazaquin)、芬布錫(fenbutatin oxide)、皮蠅硫磷(fenchlorphos)、乙苯威(fenethacarb)、五氟苯菊酯(fenfluthrin)、撲滅松(fenitrothion)、丁基滅必虱(fenobucarb)、苯硫威(fenothiocarb)、非諾克林(fenoxacrim)、芬諾克(fenoxycarb)、吡賽滅寧(fenpirithrin)、芬普寧(fenpropathrin)、芬普蟎(fenpyroximate)、除蟎酯(fenson)、豐索磷(fensulfothion)、芬殺松(fenthion)、乙基芬殺松(fenthion-ethyl)、芳氟胺(fentrifanil)、芬化利(fenvalerate)、費普尼(fipronil)、氟尼胺(flonicamid)、嘧蟎酯(fluacrypyrim)、克福隆(fluazuron)、氟苯蟲醯胺(flubendiamide)、氟蟎噻(flubenzimine)、氟脲(flucofuron)、氟環脲(flucycloxuron)、護賽寧(flucythrinate)、聯氟蟎(fluenetil)、氟芬內林(flufenerim)、氟芬隆(flufenoxuron)、三氟醚菊酯(flufenprox)、氟氯苯菊酯(flumethrin)、氟殺蟎(fluorbenside)、福化利(fluvalinate)、地蟲磷(fonofos)、複滅蟎(formetanate)、福木松(formothion)、胺甲威(formparanate)、丁苯硫磷(fosmethilan)、福司吡酯(fospirate)、福賽絕(fosthiazate)、丁硫環磷(fosthietan)、呋線威(furathiocarb)、抗蟲菊(furethrin)、糠醛(furfural)、γ賽洛寧(gamma cyhalothrin)、γHCH、合芬寧(halfenprox)、合芬隆
(halofenozide)、HCH、HEOD、飛布達(heptachlor)、庚烯磷(heptenophos)、速殺硫磷(heterophos)、六伏隆(hexaflumuron)、合賽多(hexythiazox)、HHDN、愛美松(hydramethylnon)、氰化氫、烯蟲乙酯(hydroprene)、海昆威(hyquincarb)、菸鹼硫磷(imicyafos)、吡蟲啉(imidacloprid)、依普寧(imiprothrin)、因得克(indoxacarb)、碘甲烷、IPSP、isamidofos、依殺松(isazofos)、碳氯靈(isobenzan)、水胺硫磷(isocarbophos)、異阿特靈(isodrin)、亞芬松(isofenphos)、滅必虱(isoprocarb)、亞賜圃(isoprothiolane)、獲賜松(isothioate)、加福松(isoxathion)、依維菌素(ivermectin)、茉莉菊酯I(jasmolin I)、茉莉菊酯II、碘硫磷(jodfenphos)、保幼激素I(juvenile hormone I)、保幼激素II、保幼激素III、氯戊環(kelevan)、烯蟲炔酯(kinoprene)、λ賽洛寧(lambda cyhalothrin)、砷酸鉛(lead arsenate)、林皮沒丁(lepimectin)、福賜松(leptophos)、靈丹(lindane)、啶蟲磷(lirimfos)、祿芬隆(lufenuron)、福賽絕(lythidathion)、馬拉松(malathion)、丙蟎氰(malonoben)、疊氮磷(mazidox)、滅加松(mecarbam)、甲基減蚜磷(mecarphon)、滅蚜松(menazon)、地安磷(mephosfolan)、氯化亞汞(mercurous chloride)、甲硫芬(mesulfen)、甲亞碸磷(mesulfenfos)、氰氟蟲胺(metaflumizone)、威百畝(metam)、蟲蟎畏(methacrifos)、達馬松(methamidophos)、滅大松(methidathion)、滅賜克(methiocarb)、殺蟲乙烯磷(methocrotophos)、納乃得(methomyl)、美賜平(methoprene)、甲氧滴滴涕(methoxychlor)、滅芬諾(methoxyfenozide)、溴化甲烷、異硫氰酸甲酯、甲基氯、二氯甲烷、甲氧苄氟菊酯(metofluthrin)、速滅威(metolcarb)、蟲酮(metoxadiazone)、美文松(mevinphos)、茲克威(mexacarbate)、密滅汀(milbemectin)、米爾倍黴素肟(milbemycin oxime)、丙胺氟(mipafox)、滅蟻靈(mirex)、MNAF、亞素
靈(monocrotophos)、茂果(morphothion)、莫昔克丁(moxidectin)、萘肽磷(naftalofos)、乃力松(naled)、萘、菸鹼、氟蟻靈(nifluridide)、華光黴素(nikkomycins)、烯啶蟲胺(nitenpyram)、硝乙脲噻唑(nithiazine)、戊氰威(nitrilacarb)、諾伐隆(novaluron)、多氟脲(noviflumuron)、氧樂果(omethoate)、歐殺滅(oxamyl)、甲基滅多松(oxydemeton methyl)、異亞碸磷(oxydeprofos)、碸拌磷(oxydisulfoton)、對二氯苯、巴拉松(parathion)、甲基巴拉松、氟幼脲(penfluron)、五氯苯酚、百滅寧(permethrin)、芬硫磷(phenkapton)、苯醚菊酯(phenothrin)、賽達松(phenthoate)、福瑞松(phorate)、裕必松(phosalone)、硫環磷(phosfolan)、益滅松(phosmet)、對氯硫磷(phosnichlor)、福賜米松(phosphamidon)、膦、磷蟲威(phosphocarb)、巴賽松(phoxim)、甲基巴賽松、甲胺啼磷(pirimetaphos)、比加普(pirimicarb)、乙基亞特松(pirimiphos ethyl)、甲基亞特松、亞砷酸鉀(potassium arsenite)、硫氰化鉀、pp' DDT、普亞列寧(prallethrin)、早熟素I(precocene I)、早熟素II、早熟素III、乙醯嘧啶磷(primidophos)、丙氯醇(proclonol)、布飛松(profenofos)、丙氟菊酯(profluthrin)、蜱虱威(promacyl)、猛殺威(promecarb)、丙蟲磷(propaphos)、毆蟎多(propargite)、巴胺磷(propetamphos)、安丹(propoxur)、乙噻唑磷(prothidathion)、普硫松(prothiofos)、發硫磷(prothoate)、丙苯烴菊酯(protrifenbute)、吡唑硫磷(pyraclofos)、氟蟲腈(pyrafluprole)、白粉松(pyrazophos)、反滅蟲菊(pyresmethrin)、必列寧I(pyrethrin I)、必列寧II、比達本(pyridaben)、啶蟲丙醚(pyridalyl)、嗒硫磷(pyridaphenthion)、哌氟喹腙哌氟喹腙(pyrifluquinazon)、嘧蟎醚(pyrimidifen)、嘧硫磷(pyrimitate)、派瑞樂(pyriprole)、百利普芬(pyriproxyfen)、苦木(quassia)、拜裕松(quinalphos)、拜裕松、甲基-拜裕松(quinalphos-
methyl)、畜寧磷(quinothion)、量化(quantifies)、碘醚柳胺(rafoxanide)、列滅寧(resmethrin)、魚藤精(rotenone)、魚尼丁(ryania)、沙巴藜蘆(sabadilla)、八甲磷(schradan)、司拉克丁(selamectin)、矽護芬(silafluofen)、亞砷酸鈉、氟化鈉、六氟矽酸鈉、硫氰酸鈉、蘇硫磷(sophamide)、斯平托蘭(spinetoram)、賜諾殺(spinosad)、賜派芬(spirodiclofen)、螺甲蟎酯(spiromesifen)、螺蟲乙酯(spirotetramat)、磺苯醚隆(sulcofuron)、舒非侖(sulfiram)、氟蟲胺(sulfluramid)、治螟磷(sulfotep)、硫、磺醯氟、硫丙磷(sulprofos)、tau福化利(tau fluvalinate)、噻蟎威(tazimcarb)、TDE、得芬諾(tebufenozide)、得芬瑞(tebufenpyrad)、丁基嘧啶磷(tebupirimfos)、得福隆(teflubenzuron)、七氟菊酯(tefluthrin)、亞培松(temephos)、TEPP、環戊烯丙菊酯(terallethrin)、託福松(terbufos)、四氯乙烷、樂本松(tetrachlorvinphos)、得脫蟎(tetradifon)、治滅寧(tetramethrin)、殺蟎素(tetranactin)、殺蟎好(tetrasul)、θ賽滅寧(theta cypermethrin)、賽果培(thiacloprid)、噻蟲(thiamethoxam)、苯噻硫磷(thicrofos)、抗蟲威(thiocarboxime)、硫賜安(thiocyclam)、硫敵克(thiodicarb)、硫伐隆(thiofanox)、硫滅松(thiometon)、硫磷(thionazin)、克殺蟎(thioquinox)、殺蟲雙(thiosultap)、蘇雲金素(thuringiensin)、脫芬瑞(tolfenpyrad)、泰滅寧(tralomethrin)、拜富寧(transfluthrin)、反百滅寧(transpermethrin)、苯蟎噻(triarathene)、唑蚜威(triazamate)、三落松(triazophos)、三氯松(trichlorfon)、異皮蠅磷3(trichlormetaphos 3)、壤蟲磷(trichloronat)、三氯丙氧磷(trifenofos)、三福隆(triflumuron)、混滅威(trimethacarb)、烯蟲硫酯(triprene)、繁米松(vamidothion)、繁米松、凡尼普羅(vaniliprole)、凡尼普羅、XMC、滅爾虱(xylvlcarb)、ζ賽滅寧(zeta cypermethrin)及左拉普磷(zolaprofos)。
例示性殺真菌劑包括(但不限於)活化酯、醯基胺基酸殺真菌劑、阿普泰克(acypetacs)、阿迪嗎啉(aldimorph)、脂族氮殺真菌劑、烯丙醇、醯胺殺真菌劑、氨丙膦酸(ampropylfos)、敵菌靈(anilazine)、苯胺殺真菌劑、抗生素殺真菌劑、芳族殺真菌劑、金色制酶素(aureofungin)、氧環唑、氧化福美雙(azithiram)、亞托敏(azoxystrobin)、聚硫化鋇、本達樂(benalaxyl)、本達樂-M、麥鏽靈(benodanil)、免賴得(benomyl)、醌肟腙(benquinox)、苯他隆(bentaluron)、苯噻菌胺(benthiavalicarb)、苯紮氯銨、苯瑪松(benzamacril)苯甲醯胺殺真菌劑、抑菌啉(benzamorf)、苯甲醯苯胺殺真菌劑、苯并咪唑殺真菌劑、苯并咪唑前體殺真菌劑、苯并咪唑基胺甲酸酯殺真菌劑、苯并異羥肟酸、苯并噻唑殺真菌劑、比托沙(bethoxazin)、百蟎克(binapacryl)、聯二苯、比多農(bitertanol)、硫雙二氯酚、必殺吩(bixafen)、殺稻瘟菌素-S(blasticidin-S)、硼酸、波爾多液(Bordeaux)混合物、白可列(boscalid)、橋接二苯基殺真菌劑、糠菌唑(bromuconazole)、布瑞莫(bupirimate)、勃艮第(Burgundy)混合物、丁硫啶(buthiobate)、二級丁胺、聚硫化鈣、四氯丹(captafol)、蓋普丹(captan)、胺甲酸酯殺真菌劑、嗎菌威(carbamorph)、苯氨基甲酸酯殺真菌劑、貝芬替(carbendazim)、萎鏽靈(carboxin)、加普胺(carpropamid)、香芹酮(carvone)、切欣特(Cheshunt)混合物、蟎離丹(chinomethionat)、克氯綜(chlobenthiazone)、雙胺靈(chloraniformethan)、四氯醌(chloranil)、克凡唑(chlorfenazole)、氯二硝萘(chlorodinitronaphthalene)、氯仿、地茂散(chloroneb)、氯化苦(chloropicrin)、四氯異苯腈(chlorothalonil)、四氯喹惡啉(chlorquinox)、克氯得(chlozolinate)、環吡酮(ciclopirox)、甘寶素(climbazole)、克黴唑(clotrimazole)、康唑殺真菌劑(conazole fungicides)、康唑殺真菌劑(咪唑)、康唑殺真菌劑(三唑)、乙酸銅(II)、碳酸酯銅(II)、鹼、銅殺真菌劑、氫氧
化銅、環烷酸銅、油酸銅、鹼性氯氧化銅、硫酸銅(II)、硫酸銅、鹼、鉻酸銅鋅、甲酚、硫雜靈(cufraneb)、福美銅氯(cuprobam)、氧化亞銅、賽座滅(cyazofamid)、環菌胺(cyclafuramid)、環狀二硫代胺甲酸酯殺真菌劑、環己醯亞胺、環氟菌胺(cyflufenamid)、克絕(cymoxanil)、氰菌靈(cypendazole)、環克座(cyproconazole)、賽普洛(cyprodinil)、邁隆(dazomet)、DBCP、咪菌威(debacarb)、癸磷錫(decafentin)、去氫乙酸、二甲醯亞胺殺真菌劑、益發靈(dichlofluanid)、大克隆(dichlone)、二氯酚(dichlorophen)、二氯苯基、菌核利(dichlozoline)、苄氯三唑醇(diclobutrazol)、二氯西莫(diclocymet)、達滅淨(diclomezine)、氯硝胺(dicloran)、乙黴威(diethofencarb)、焦碳酸二乙酯、待克利(difenoconazole)、二氟林(diflumetorim)、二甲嘧酚(dimethirimol)、達滅芬(dimethomorph)、地莫菌胺(dimoxystrobin)、達克利(diniconazole)、達克利-M、二硝基苯酚殺真菌劑、大脫蟎(dinobuton)、白粉克、白粉克-4、白粉克-6、鄰敵蟎消(dinocton)、硝戊酯(dinopenton)、硝辛酯(dinosulfon)、硝丁酯(dinoterbon)、二苯胺、雙硫氧吡啶(dipyrithione)、二硫龍(disulfiram)、滅菌磷(ditalimfos)、腈硫醌(dithianon)、二硫代胺甲酸酯殺真菌劑、DNOC、嗎菌靈(dodemorph)、多地辛(dodicin)、多寧(dodine)、多納托定(donatodine)、敵菌酮(drazoxolon)、護粒松(edifenphos)、依普座(epoxiconazole)、乙環唑(etaconazole)、代森硫(etem)、噻唑菌胺(ethaboxam)、依瑞莫(ethirimol)、乙氧喹、環氧乙烷、2,3-二羥丙基硫醇乙基汞、乙酸乙基汞、溴乙基汞、氯乙基汞、磷酸乙基汞、依得利(etridiazole)、凡殺同(famoxadone)、咪唑菌酮(fenamidone)、敵克松(fenaminosulf)、咪菌腈(fenapanil)、芬瑞莫(fenarimol)、芬克座(fenbuconazole)、甲呋醯胺(fenfuram)、環醯菌胺(fenhexamid)、種衣酯
(fenitropan)、氰菌胺(fenoxanil)、拌種咯(fenpiclonil)、苯鏽啶(fenpropidin)、芬普福(fenpropimorph)、三苯錫(fentin)、福美鐵(ferbam)、富米綜(ferimzone)、扶吉胺(fluazinam)、氟康唑(Fluconazole)、護汰寧(fludioxonil)、氟醯菌胺(flumetover)、氟嗎啉(flumorph)、氟吡菌胺(fluopicolide)、唑呋草(fluoroimide)、三氟苯唑(fluotrimazole)、氟嘧菌酯(fluoxastrobin)、氟喹唑(fluquinconazole)、護矽得(flusilazole)、氟硫滅(flusulfamide)、福多寧(flutolanil)、護汰芬(flutriafol)、氟唑菌醯胺(fluxapyroxad)、福爾培(folpet)、甲醛、福賽得(fosetyl)、麥穗靈(fuberidazole)、呋霜靈(furalaxyl)、福拉比(furametpyr)、糠醯胺(furamide)殺真菌劑、糠苯胺(furanilide)殺真菌劑、二甲呋醯胺(furcarbanil)、呋菌唑(furconazole)、順式呋菌唑(furconazole-cis)、糠醛、茂谷樂(furmecyclox)、呋菌隆(furophanate)、果綠定(glyodin)、灰黃黴素(griseofulvin)、雙胍鹽、丙烯酸喹啉酯(halacrinate)、六氯苯、六氯丁二烯、六氯酚、菲克利(hexaconazole)、己硫松(hexylthiofos)、汞加芬(hydrargaphen)、惡黴靈(hymexazol)、依滅列(imazalil)、亞胺唑(imibenconazole)、咪唑殺真菌劑、克熱淨(iminoctadine)、無機殺真菌劑、無機汞殺真菌劑、碘甲烷、種菌唑(ipconazole)、丙基喜樂松(iprobenfos)、依普同(iprodione)、纈黴威(iprovalicarb)、異丙醇、稻瘟靈(isoprothiolane)、異凡二酮(isovaledione)、吡唑萘菌胺(isopyrazam)、春日黴素(kasugamycin)、酮康唑(ketoconazole)、克收欣(kresoxim-methyl)、石灰硫(Lime sulfur/lime sulphur)、代森錳銅(mancopper)、鋅錳乃浦(mancozeb)、錳乃浦(maneb)、滅鏽胺(mebenil)、苯并威(mecarbinzid)、嘧菌胺(mepanipyrim)、滅普寧(mepronil)、氯化汞(作廢)、氧化汞(作廢)、氯化亞汞(作廢)、滅達樂
(metalaxyl)、滅達樂-M(亦稱為精甲霜靈(Mefenoxam))、威百畝(metam)、間氯敵菌酮(metazoxolon)、滅特座(metconazole)、滅速克(methasulfocarb)、呋菌胺(methfuroxam)、溴化甲烷、異硫氰酸甲酯、苯甲酸甲基汞、二氰二胺甲基汞、五氯酚甲基汞、免得爛(metiram)、苯氧菌胺(metominostrobin)、滅芬農(metrafenone)、噻菌胺(metsulfovax)、代森環(milneb)、嗎啉殺真菌劑、邁克尼(myclobutanil)、米克啉(myclozolin)、N-(乙基汞)-對-甲苯磺醯苯胺、代森鈉(nabam)、遊黴素(natamycin)、制真菌素(nystatin)、β-硝基苯乙烯、酞菌酯(nitrothal-isopropyl)、尼瑞莫(nuarimol)、OCH、辛噻酮(octhilinone)、呋醯胺(ofurace)、奧普地酮(oprodione)、有機汞殺真菌劑、有機磷殺真菌劑、有機錫殺真菌劑(作廢)、鄰苯基苯酚、肟醚菌胺(orysastrobin)、歐殺斯(oxadixyl)、噻殺真菌劑、唑殺真菌劑、快得寧(oxine copper)、噁咪唑(oxpoconazole)、嘉保信(oxycarboxin)、披扶座(pefurazoate)、平克座(penconazole)、賓克隆(pencycuron)、五氯苯酚、吡噻菌胺(penthiopyrad)、苯汞脲(phenylmercuriurea)、乙酸苯基汞、氯苯基汞、鄰苯二酚之苯基汞衍生物、硝酸苯基汞、水楊酸苯基汞、苯基硫醯胺殺真菌劑、氯瘟磷(phosdiphen)、亞磷酸酯、苯酞、鄰苯二甲醯亞胺殺真菌劑、啶氧菌酯(picoxystrobin)、粉病靈(piperalin)、聚胺甲酸酯、聚合二硫代胺甲酸酯殺真菌劑、多氧菌素(polyoxins)、保粒黴素(polyoxorim)、聚硫化物殺真菌劑、疊氮化鉀、聚硫化鉀、硫氰化鉀、撲殺熱(probenazole)、咪醯胺(prochloraz)、撲滅寧(procymidone)、霜黴威(propamocarb)、普克利(propiconazole)、甲基鋅乃浦(propineb)、丙氧喹啉(proquinazid)、硫菌威(prothiocarb)、丙硫菌唑(prothioconazole)、比鏽靈(pyracarbolid)、百克敏(pyraclostrobin)、吡唑殺真菌劑、白粉松、吡啶殺真菌劑、啶菌腈(pyridinitril)、比芬諾(pyrifenox)、
嘧黴胺(pyrimethanil)、嘧啶殺真菌劑、百快隆(pyroquilon)、吡氯靈(pyroxychlor)、吡氧呋(pyroxyfur)、吡咯殺真菌劑、羥基喹啉基乙酮(quinacetol)、醌菌腙(quinazamid)、喹唑、喹啉殺真菌劑、甲基克殺蟎(quinomethionate)、醌殺真菌劑、喹喏啉殺真菌劑、快諾芬(quinoxyfen)、五氯硝基苯(quintozene)、吡咪唑(rabenzazole)、水楊醯苯胺(salicylanilide)、矽硫芬(silthiofam)、銀、矽氟唑(simeconazole)、疊氮化鈉、碳酸氫鈉[2][3]、鄰苯基苯氧化鈉、五氯酚鈉、聚硫化鈉、螺環菌胺(spiroxamine)、鏈黴素(streptomycin)、嗜毬果傘素(strobilurin)殺真菌劑、硫醯苯胺殺真菌劑、硫、磺醯氟、戊苯碸(sultropen)、TCMTB、得克利(tebuconazole)、克枯爛(tecloftalam)、四氯硝基苯(tecnazene)、福美雙聯(tecoram)、四克利(tetraconazole)、腐絕(thiabendazole)、噻噠氟(thiadifluor)、噻唑殺真菌劑、噻菌腈(thicyofen)、賽氟滅(thifluzamide)、瑞香草酚(thymol)、賽福寧(triforine)、硫代胺甲酸酯殺真菌劑、硫氯苯亞胺(thiochlorfenphim)、硫柳汞(thiomersal)、多保淨(thiophanate)、甲基托布津(thiophanate-methyl)、噻吩殺真菌劑、克殺蟎(thioquinox)、得恩地(thiram)、汰敵寧(tiadinil)、替系米(tioxymid)、替維多(tivedo)、甲基脫克松(tolclofos-methyl)、托萘酯(tolnaftate)、甲基益發靈(tolylfluanid)、乙酸甲苯汞、三泰芬(triadimefon)、三泰隆(triadimenol)、威菌磷(triamiphos)、嘧菌醇(triarimol)、丁三唑、三嗪殺真菌劑、三唑殺真菌劑、咪唑嗪、氧化三丁基錫、水楊菌胺(trichlamide)、三環唑(tricyclazole)、三得芬(tridemorph)、三氟敏(trifloxystrobin)、賽福座(triflumizole)、賽福寧(triforine)、滅菌唑(triticonazole)、類別不明殺真菌劑、十一碳烯酸、烯效唑(uniconazole)、烯效唑-P、脲殺真菌劑、維利微素(validamycin)、纈胺醯胺(valinamide)殺真菌劑、免克寧(vinclozolin)、伏立康唑(voriconazole)、氰菌胺(zarilamid)、
環烷酸鋅、鋅乃浦(zineb)、益穗(ziram)及/或座賽胺(zoxamide)。
殺蟎劑之例示性類別包括(但不限於)植物殺蟎劑(acaricide)、橋接二苯基殺蟎劑、胺基甲酸酯殺蟎劑、肟胺基甲酸酯殺蟎劑、肼甲酸酯殺蟎劑、二硝基苯酚殺蟎劑、甲脒殺蟎劑、依索啉(isoxaline)殺蟎劑、巨環內酯殺蟎劑、阿巴汀(avermectin)殺蟎劑、米爾倍黴素殺蟎劑、米爾倍黴素殺蟎劑、蟎生長調節因子、有機氯殺蟎劑、有機磷酸鹽殺蟎劑、有機硫代磷酸鹽殺蟎劑、膦酸酯殺蟎劑、磷醯胺硫醇酯殺蟎劑、有機錫殺蟎劑、苯基磺醯胺殺蟎劑、吡唑甲醯胺殺蟎劑、擬除蟲菊醚殺蟎劑、四級銨殺蟎劑、擬除蟲菊酯殺蟎劑、吡咯殺蟎劑、喹喏啉殺蟎劑、甲氧基丙烯酸酯嗜毬果傘素殺蟎劑、特窗酸(tetronic acid)殺蟎劑、四氫噻唑殺蟎劑、硫胺基甲酸酯殺蟎劑、硫脲殺蟎劑及未分類殺蟎劑。對於此等類別之殺蟎劑之實例包括但不限於植物殺蟎劑-香芹酚、血根鹼(sanguinarine);橋接二苯基殺蟎劑-偶氮苯、苯蟎特(benzoximate)、苯甲基、苯甲酸酯、溴蟎酯(bromopropylate)、氯殺蟎(chlorbenside)、殺蟎醇(chlorfenethol)、殺蟎酯(chlorfenson)、敵蟎特(chlorfensulphide)、乙酯殺蟎醇(chlorobenzilate)、丙酯殺蟎醇(chloropropylate)、丁氟蟎酯(cyflumetofen)、DDT、開樂散(dicofol)、二苯基、碸、苯氧炔蟎(dofenapyn)、除蟎酯(fenson)、芳氟胺(fentrifanil)、氟殺蟎(fluorbenside)、格蟎酯(genit)、六氯酚carbaryl、苯蟎醚(phenproxide)、丙氯醇、四氯殺蟎碸(tetradifon)、殺蟎好(tetrasul);胺基甲酸酯殺蟎劑-苯菌靈、氯滅殺威、加保利、加保扶、滅蟲威、速滅威、蜱虱威、安丹;肟胺基甲酸酯殺蟎劑-涕滅威、丁酮威、殺線威、抗蟲威、久效威;肼甲酸酯殺蟎劑-聯苯肼酯;二硝基酚殺蟎劑-樂殺蟎、消蟎酚、敵蟎通、敵蟎普、敵蟎普-4、敵蟎普-6、鄰敵蟎消、硝戊酯、硝辛酯、硝丁酯、DNOC;甲脒殺蟎劑-雙甲脒、殺蟲脒、滅蟎眯、伐蟲脒、胺甲威、殺蟎脒;異唑啉殺蟎劑-阿福拉納
(afoxolaner)、氟雷拉納(fluralaner)、洛替拉納(lotilaner)、薩洛拉納(sarolaner);巨環內酯殺蟎劑-殺蟎素;阿巴汀殺蟎劑-阿巴克丁、多拉克汀、依立諾克汀、伊維克汀、司拉克汀;米爾倍黴素殺蟎劑-密滅汀、米爾倍黴素、肟、莫昔克丁;蟎生長調節因子-四蟎、賽滅淨、氟蟎、苯氧炔蟎、啶蜱脲、氟蟎噻、氟環脲、氟芬隆、噻蟎酮;有機氯殺蟎劑-溴西克林、毒殺芬、DDT、除蟎靈、硫丹、林丹;有機磷酸酯殺蟎劑-毒蟲畏、巴毒磷、二氯松、庚烯磷、速滅磷、久效磷、二溴磷、TEPP、司替羅磷;有機硫代磷酸酯殺蟎劑-賽果、胺吸磷、乙基穀硫磷、甲基穀硫磷、偶氮磷、解草、溴硫磷、乙基溴硫磷、三硫磷、毒死蜱、蟲蟎磷、蠅毒磷、果蟲磷、內吸磷、內吸磷-O、內吸磷-S、甲基內吸磷、內吸磷-O-甲基、內吸磷-S-甲基、內吸磷-S-甲磺酸、氯亞胺硫磷、二磷、大滅松、敵殺磷、二硫松、因毒磷、抑草威、甲基益果、安果、馬拉松、滅蚜磷、蟲蟎畏、氧樂果、異亞碸磷、碸拌磷、巴拉松、芬硫磷、福瑞松、裕必松、亞胺硫磷、三磷錫、巴賽松、甲基亞特松、乙噻唑磷、發硫磷、嘧硫磷、拜裕松、喹硫磷(quintiofos)、蘇硫磷、治螟磷、甲基乙拌磷、三落松、三氯丙氧磷、蚜滅多;膦酸酯殺蟎劑-三氯松;硫代磷醯胺殺蟎劑-水胺硫磷、達馬松、胺丙畏;磷二醯胺殺蟎劑-甲氟磷、丙胺氟、八甲磷;有機錫殺蟎劑-三唑錫、殺蟎錫、氧化苯丁錫(fenbutatin,oxide)、三磷錫;苯基硫醯胺殺蟎劑-苯氟磺胺;鄰苯二甲醯亞胺殺蟎劑-氯亞胺硫磷、亞胺硫磷;吡唑殺蟎劑-腈吡蟎酯、唑蟎酯;苯基吡唑殺蟎劑-乙醯蟲腈、氟蟲腈、凡尼普羅;吡唑甲醯胺殺蟎劑-吡氟丁醯胺(pyflubumide)、吡蟎胺;擬除蟲菊酯殺蟎劑-氟丙菊酯、聯苯菊酯、溴氟菊酯(brofluthrinate)、賽洛寧、賽滅寧、α-賽滅寧、芬普寧、芬化利、護賽寧、氟氯苯菊酯、氟胺氰菊酯、τ-氟胺氰菊酯、百滅寧;擬除蟲菊醚殺蟎劑-苄蟎醚;胺基嘧啶殺蟎劑-嘧蟎醚;吡咯殺蟎劑-克凡派;四級銨殺蟎劑-血根鹼;喹啉殺蟎劑-滅蟎猛、克殺蟎;甲氧基丙烯酸酯
嗜毬果傘素殺蟎劑-吡氟菌酯(bifujunzhi)、嘧蟎酯、氟菌蟎酯(flufenoxystrobin)、嘧蟎胺(pyriminostrobin);亞硫酸酯殺蟎劑-殺蟎特、毆蟎多;特窗酸殺蟎劑-螺蟎酯;四殺蟎劑,四蟎、氟蟎;噻唑啶殺蟎劑-氟蟎噻、噻蟎酮;硫胺基甲酸酯殺蟎劑-苯硫威;硫脲殺蟎劑-滅蟲脲、丁醚脲;未分類殺蟎劑-亞醌蟎、阿克諾派、磺胺蟎酯、氧化砷(arsenous,oxide)、克侖吡林、氯氰碘柳胺、克羅米通、環蟎酯、蟎蜱胺、二硫侖、依殺蟎、抗蟎唑、喹蟎醚、聯氟蟎、甲硫芬、MNAF、氟蟻靈、尼可黴素、噠蟎靈、舒非侖、氟蟲胺、硫、蘇雲金素、苯蟎噻。
在一些實施例中,殺蟎劑亦可以選自阿巴汀、歐殺松、亞醌蟎、亞滅培、得滅克、亞列寧、磷化鋁、滅害威、三亞蟎、印楝素(azadiractin)、乙基穀硫磷(azinphos-ethyl)、甲基穀硫磷(azinphos-methyl)、蘇力菌(Bacillus thuringiensis)、惡蟲威、β-賽扶寧(beta-cyfluthrin)、畢芬載、畢芬甯、保米磷(bomyl)、布芬淨、氰化鈣、加保利、加保扶、二硫化碳、四氯化碳、克芬松、乙酯殺蟎醇(chlorobenzilate)、氯化苦、陶斯松、克芬蟎、克凡派、可尼丁、蠅毒磷、巴毒磷、巴毒磷+二氯松、冰晶石、賽扶寧、賽滅淨、賽滅寧、避蚊胺(deet)、第滅寧、內吸磷、大利松、除線磷、二氯丙烯、二氯松、開樂散、雙特松、狄氏劑、除蟎靈、二福隆、錳鋅敵混劑(dikar)(殺真菌劑+殺蟎劑)、大滅松、白粉克、呋蟲胺、敵殺磷、二硫松、苯甲酸因滅汀(emamectin benzoate)、安殺番、安特靈、益化利、愛殺松、滅克磷、二溴化乙烯、二氯化乙烯、依殺蟎、伐滅磷、撲滅松、芬諾克、芬普寧、芬普蟎、豐索磷、芬殺松、芬化利、氟啶蟲醯胺、護賽寧、福化利、地蟲磷、鹽酸複滅蟎(formetanate hydrochloride)、γ-賽洛寧(gamma-cyhalothrin)、合芬隆、苯丙錫(hexakis)、合賽多、愛美松、熟石灰(hydrated lime)、因得克、吡蟲啉(imidacloprid)、煤油(kerosene)、烯蟲炔酯、λ-賽洛
寧(lambda-cyhalothrin)、砷酸鉛、靈丹、馬拉松、地安磷、聚乙醛(metaldehyde)、威百畝-鈉(metam-sodium)、達馬松、滅大松、滅賜克、納乃得、美賜平、甲氧滴滴涕、滅芬諾、溴化甲烷、甲基巴拉松(methyl parathion)、美文松、茲克威、乳狀孢子病(milky spore disease)、乃力松、萘、硫酸尼古丁(nicotine sulfate)、諾伐隆、歐殺滅、甲基滅多松(oxydemeton-methyl)、滅蟎猛、對二氯苯(para-dichlorobenzene)、巴拉松、PCP、百滅寧、石油、福瑞松、裕必松、硫環磷、益滅松、福賜米松、巴賽松、胡椒基丁醚(piperonyl butoxide)、比加普、甲基亞特松(pirimiphos-methyl)、布飛松、毆蟎多、巴胺磷、安丹、派滅淨、合成擬除蟲菊酯(pyrethroids-synthetic):參見亞列寧、百滅寧、芬化利、苄呋菊脂、除蟲菊(pyrethrum)、比達本、百利普芬、苄呋菊脂、魚藤酮、s-美賜平(s-methoprene)、農藥皂(soap,pesticidal)、氟化鈉、賜諾殺、螺甲蟎酯、治螟磷、硫丙磷、雙硫磷、託福松、樂本松、樂本松+二氯松、四氯殺蟎碸、噻蟲、硫敵克、毒殺芬(toxaphene)、泰滅寧、混滅威及得芬諾。
含有額外活性劑(例如農藥、除草劑、殺昆蟲劑、殺真菌劑及/或殺蟎劑)之農業組合物中之氮穩定組合物的量可以變化。在一些實施例中,以含有視為100重量%之額外活性劑的農業組合物之總重量計,氮穩定組合物之量以約0.05重量%-10重量%(或約0.1重量%-8重量%;或約0.1重量%-4重量%,且最佳約0.2重量%-2重量%)之位準存在。
V.方法
在一些實施例中,氮穩定組合物及/或調配物直接使用。在其他實施例中,氮穩定組合物以使得其在生產性農業之情形下使用方便之方式調配。此等方法中所使用之氮穩定組合物包括如上文所描述之氮穩定劑組分及環狀有機酸酐組分。氮穩定組合物可以用於諸如以下之方法:
A.改良植物生長及/或對土壤施肥之方法
B.抑制硝化、脲酶分解或氨釋放或逸出之方法
C.改良土壤條件之方法
D.改良農作物產量之方法
E.製備氮穩定組合物之方法
F.製備氮穩定組合物之調配物之方法
A.改良植物生長之方法包含使含有如本文所揭示之氮穩定組合物之氮穩定組合物或調配物與土壤接觸。在一些實施例中,將氮穩定組合物或調配物在種植作物出苗之前施用於土壤。在一些實施例中,將氮穩定組合物或調配物施用於與植物相鄰之土壤及/或植物之底部及/或植物之根部區。
改良植物生長之方法亦可以藉由將如本文所揭示之氮穩定組合物或含有氮穩定組合物之調配物作為種子包衣以液體分散液形式施用至種子來達成,該液體分散液在乾燥後形成乾燥殘餘物。在此等實施例中,種子包衣在種植時提供非常接近於種子之氮穩定組合物,以使得氮穩定組合物可以在最需要其之環境中發揮其有益作用。亦即,氮穩定組合物在可以使作用定位於所需植物周圍之區域中提供有利於增強植物生長之環境。在種子之情況下,含有氮穩定組合物之塗層為種子發芽、後續植物生長提供增強的機會且提高植物養分可用性。
B.用於抑制/減少受影響區域中之硝化、脲酶分解或氨釋放或逸出之方法包含向受影響區域施用如本文所揭示之氮穩定組合物或含有氮穩定組合物之調配物。受影響區域可為鄰近植物之土壤、田地、牧草、家畜或家禽約束設施、寵物墊料、糞肥採集區、形成圍欄之豎直牆壁或基本上覆蓋該區域之頂蓋,且在此等情況下可將氮穩定組合物直接施用至採集區中之糞肥。本文所揭示之方法亦關於抑制脲轉化為氨及/或氨轉化為硝酸鹽,其包含向受影響區域
施用如本文所揭示之氮穩定組合物或含有氮穩定組合物之調配物。組合物較佳以約0.005-3加侖/公噸糞肥之位準施用,呈pH為約1-5之水性分散液形式。
C.用於改良選自由硝化過程、脲酶活性及其組合組成之群之土壤條件的方法,其包含向土壤施用有效量的所描述之氮穩定組合物或其調配物之步驟。在一些實施例中,將氮穩定組合物與固體、液體或氣態肥料及尤其固體肥料混合;在後一情況下,將氮穩定組合物以水性分散液形式施用至肥料表面,隨後乾燥,以使得氮穩定組合物以乾燥殘餘物形式存在於固體肥料上。以視為100重量%之氮穩定組合物/肥料產品之總重量計,氮穩定組合物一般以約0.01%-10重量%之位準施用。當肥料為水性液體肥料時,伴以混合將氮穩定組合物添加至其中。氮穩定組合物較佳在水性分散液中且具有至多約3之pH。
D.改良農作物產量之方法包含將如本文所揭示之氮穩定組合物或含有氮穩定組合物的調配物施加至受影響區域。在一些實施例中,受影響區域可為田地。在一些實施例中,將氮穩定組合物或調配物施加至植物周圍土壤,鄰近於植物莖,或噴灑至植物之不同植物部分上。在一些實施例中,植物為玉蜀黍植物,儘管其不應限於此。在一些實施例中,將氮穩定組合物或調配物與肥料組合施用。在一些實施例中,肥料為含氮肥料。在一些實施例中,肥料含有脲。在一些實施例中,在施用含氮肥料之前、之後或同時,施用含氮組合物或調配物。在一些實施例中,經如本文所揭示之氮穩定組合物處理之植物的農作物產量/收穫產量相比於未經處理之植物,增加至少約10%、約20%、約30%、約40%、約50%、約60%、約70%、約80%、約90%,或至少約95%。在一些實施例中,經如本文所揭示之氮穩定組合物處理之植物的農作物/收穫產量相比於未經處理之植物,增加約50%至約100%、約60%至約95%、約65%至約95%、約65%至約90%、約65%至約80%,或約70%至約80%。在一些實施例中,將氮穩定組合物與脲組合施用。在一些實施例中,經如本文所揭示之氮穩
定組合物與脲組合處理之植物的農作物/收穫產量相比於經脲處理之植物,增加至少約1%、約5%、約8%、約10%、約12%、約14%、約15%、約18%、約20%、約22%、約24%、約25%。在一些實施例中,經如本文所揭示之氮穩定組合物與脲組合處理之植物的農作物/收穫產量相比於經脲處理之植物,增加約1%至約30%、約1%至約25%、約5%至約25%、約15%至約25%、約20%至約25%、約5%至約20%,或約5%至約15%。
在一些實施例中,相比於存在於來自未經處理之玉蜀黍植物的玉米穗軸上的穀粒之列數,存在於來自經所揭示之調配物處理之玉蜀黍植物的玉米穗軸上的穀粒之列數更高。在一些實施例中,相比於存在於未經處理之玉蜀黍植物之玉米穗中的穀粒之列數,存在於來自經如本文所揭示之氮穩定組合物或調配物處理之玉蜀黍植物之玉米穗中的穀粒之列數多至少約10%、約20%、約30%、約40%、約50%、約60%、約70%或約80%。在一些實施例中,相比於存在於未經處理玉蜀黍植物之玉米穗中的穀粒之列數,存在於來自經如本文所揭示之氮穩定組合物或調配物處理之玉蜀黍植物之玉米穗中的穀粒之列數高約10%至約80%、約20%至70%、約30%至約60%,或約40%至約50%。
在一些實施例中,相比於存在於經氮肥(亦即,脲)處理之玉蜀黍植物之玉米穗中的穀粒之列數,存在於來自經如本文所揭示之氮穩定組合物或調配物與氮肥組合處理之玉蜀黍植物之玉米穗中的穀粒之列數高至少約10%、約20%、約30%、約40%、約50%、約60%、約70%或約80%。在一些實施例中,相比於存在於經氮肥(亦即,脲)處理之玉蜀黍植物之玉米穗中的穀粒之列數,存在於來自經如本文所揭示之氮穩定組合物或調配物處理之玉蜀黍植物之玉米穗中的穀粒之列數高約10%至約80%、約20%至70%、約25%至約60%、約30%至約50%,或約30%至約40%。
E.製備如本文所揭示之氮穩定組合物之方法包含使氮穩定劑組
分與酸酐組分接觸。接觸步驟可以在無溶劑下進行或可以在溶劑存在下進行。在一些實施例中,接觸步驟進一步包含非極性溶劑,諸如但不限於乙腈。在一些實施例中,接觸步驟在環境溫度下進行。在一些實施例中,接觸步驟若在約25℃至約150℃、約30℃至約120℃、約40℃至約100℃、約50℃至約90℃,或約60℃至約80℃範圍內之高溫下進行。氮穩定劑組分及酸酐組分之量可以變化。在一些實施例中,氮穩定劑組分及酸酐組分以約1:2至約2:1範圍內之莫耳比存在。
F.製備氮穩定組合物之穩定調配物的方法揭於示本文中。為了製備如本文所揭示之調配物,該等方法需要完全溶解存在於調配物中之所有組分。包括使氮穩定組分與作為如本文所揭示之聚合物的有機酸酐組分在非質子性溶劑存在下接觸的方法在得到所需調配物中不成功,因為並非所有組分(尤其聚合物)均可溶於在室溫下以及在高溫下的非質子性溶劑中。出乎意料地,僅在首先製備以高濃度存在之聚合物的預混合溶液時獲得所需調配物,且隨後自其移除等分試樣,其隨後用額外非質子性溶劑稀釋且與氮穩定組合物接觸。極令人驚奇且出人意料地發現,當聚合物首先製備為預混合溶液,隨後將聚合物與氮穩定劑組分混合時,氮穩定組合物之所有組分僅為可溶的。
因此,製備如本文所揭示之調配物的方法包含以下步驟:將有機酸酐組分與第一非質子性溶劑混合以形成有機酸酐組分預混合溶液;取出有機酸酐組分預混合溶液之等分試樣;用第二非質子性溶劑稀釋所取出之等分試樣以得到有機酸酐溶液;使有機酸酐溶液與胺穩定劑接觸以得到穩定有機酸酐溶液;及向穩定有機酸酐溶液中添加氮穩定劑組分以得到所需穩定調配物。
在一些實施例中,有機酸酐組分為如本文所揭示之聚合物。在
一些實施例中,第一非質子性溶劑及第二非質子性溶劑相同。在一些實施例中,第一非質子性溶劑為DMSO。在一些實施例中,混合步驟在高溫(例如高於室溫)下進行。在一些實施例中,混合步驟在約30℃至約200℃、約40℃至約175℃、約50℃至約150℃、約60℃至約125℃、約70℃至約100℃,或約75℃至約85℃範圍內之溫度下進行。在一些實施例中,混合步驟在室溫下進行。應注意,有機酸酐組分在室溫下溶劑化比其在高溫下溶劑化更慢。在一些實施例中,以有機酸酐組分預混合溶液之總重量計,待混合之有機酸酐組分之量在約5%至約25% w/w範圍內。
在一些實施例中,以有機酸酐組分預混合溶液之總重量計,取出步驟中之有機酸酐組分預混合溶液之等分試樣之量在約25%至約50% w/w範圍內。
在一些實施例中,以穩定調配物之總重量計,第二非質子性溶劑之量在約20%至約50% w/w範圍內。在一些實施例中,第二非質子性溶劑為DMSO。
在一些實施例中,以穩定調配物之總重量計,胺穩定劑之量在約1%至約20% w/w範圍內。在一些實施例中,胺穩定劑為單乙醇胺。
在一些實施例中,氮穩定劑組分為脲酶抑制劑及/或硝化抑制劑。在一些實施例中,氮穩定劑組分為DCD。在一些實施例中,氮穩定劑組分為NBPT。
在一些實施例中,氮穩定劑組分為NBPT及DCD。在此等實施例中,該方法進一步包含將DCD及NBPT逐次添加至穩定有機酸酐溶液中。舉例而言,在一些實施例中,在NBPT之前將DCD添加至穩定有機酸酐溶液中。在一些實施例中,該方法進一步包含在添加DCD之後且在添加NBPT之前冷卻穩定有機酸酐溶液。在一些實施例中,在添加DCD之後但在添加NBPT之前,
使穩定有機酸酐溶液冷卻約80℃或更低。
本文所揭示之方法亦係關於製備氮穩定組合物之個別組分的穩定調配物,其包含以下步驟:使胺穩定劑與非質子性溶劑接觸以得到穩定非質子性溶劑;及將氮穩定劑組分添加至穩定非質子性溶劑中以得到穩定調配物。
本文所揭示之方法亦係關於製備含有如本文所揭示之有機酸酐組分之穩定調配物,其包含以下步驟:使有機酸酐組分與第一非質子性溶劑混合以形成有機酸酐組分預混合溶液;取出有機酸酐組分預混合溶液之等分試樣;用第二非質子性溶劑稀釋所取出之等分試樣以得到有機酸酐溶液;將有機酸酐溶液與胺穩定劑接觸以得到穩定調配物。
在一些實施例中,以上方法A、B及C包含使所需區域與氮穩定組合物在氮穩定組合物每英畝約100g至約120g之速率下接觸。在一些實施例中,氮穩定組合物可以以約0.5磅至約4磅/美制加侖,或約1磅至約3磅/美制加侖,或約2磅/美制加侖之量處於溶液中。在一些實施例中,方法包括以約0.5至約4qt/英畝或約1至約2qt/英畝之比率接觸所需區域。
本文所描述之標的物之特定實施例包括:
1.一種穩定調配物,其包含:一種氮穩定組合物,其包含:氮穩定劑組分,及有機酸酐組分,其中該氮穩定劑組分為脲酶抑制劑及/或硝化抑制劑;及媒劑,其包含:
非質子性溶劑,及胺穩定劑。
2.如實施例1之穩定調配物,其中該氮穩定劑組分為N-(正丁基)硫代磷酸三醯胺(NBPT)及/或二氰胺(DCD)。
3.如實施例1或2之穩定調配物,其中該有機酸酐組分為有機酸酐聚合物。
4.如上述任何實施例之穩定調配物,其中該有機酸酐聚合物為含有至少兩種不同重複單元,包括B型重複單元中之一者及C型重複單元中之一者的共聚物。
5.如實施例4之穩定調配物,其中該共聚物為無規共聚物。
6.如實施例4或5之穩定調配物,其中該B型重複單元衍生自順丁烯二酸酐、伊康酸酐或其組合之(未)經取代之單體。
7.如實施例4至6中任一項之穩定調配物,其中該B型重複單元衍生自(未)經取代之順丁烯二酸酐單體。
8.如實施例4至7中任一項之穩定調配物,其中該有機酸酐聚合物之至少約50莫耳%之該等重複單元為B型重複單元。
9.如實施例4至8中任一項之穩定調配物,其中該有機酸酐聚合物含有衍生自(未)經取代之烯烴的C型重複單元。
10.如實施例9之穩定調配物,其中該烯烴係選自乙烯、丙烯、丁烯、異丁烯、苯乙烯、甲基乙烯醚及其組合。
其中R1、R2、R3及R4獨立地選自-H、-COOH、-COOR、-OCOH、-OCOR、-OR、-CN、-SO2R、-SO3R、-COR、-CONH2、-CONHR、-CONR2、-CHO、NO2、鹵素、-烷基、-環烷基、-芳基、-烷芳基或芳烷基,其中R為未經取代之C1-C8烷基、未經取代之C2-C8烯基、未經取代之芳基、未經取代之雜芳基;且n為大於2之整數。
12.如上述任何實施例之穩定調配物,其中該非質子性溶劑係選自二氯甲烷、二甲基乙醯胺、二甲基甲醯胺、二甲亞碸(DMSO)、乙酸乙酯、丙酮、乙腈、六甲基磷醯胺、二甲碸、環丁碸、1,3-二甲基-2-咪唑啶酮、1,3-二甲基-3,4,5,6-四氫-2(1 H)-嘧啶酮、乙酸甲酯、乳酸乙酯、N-甲基吡咯啶酮、四氫呋喃及碳酸伸丙酯。
13.如上述任何實施例之穩定調配物,其中該非質子性溶劑為二甲亞碸(DMSO)。
14.如上述任何實施例之穩定調配物,其中該胺穩定劑係選自1,2-二胺基環己烷(DCH)、雙(六亞甲基)三胺(BHT)、單乙醇胺、乙胺基乙醇、二甲胺基乙醇、異丙基胺基乙醇、二乙醇胺、三乙醇胺、甲胺基乙醇、胺基丙醇、甲胺基丙醇、二甲胺基丙醇、胺基丁醇、二甲胺基丁醇、胺基丁二醇、三羥甲胺基乙烷、二乙胺基丙二醇、1-胺基-環戊烷甲醇及胺基苯甲醇。
15.如上述任何實施例之穩定調配物,其中該胺穩定劑為單乙醇胺。
16.如上述任何實施例之穩定調配物,其中以該穩定調配物之總重量計,該氮穩定組合物係以約5%至約50% w/w之量存在。
17.如上述任何實施例之穩定調配物,其中以該穩定調配物之總重量計,該非質子性溶劑係以約50%至約75% w/w之量存在。
18.如上述任何實施例之穩定調配物,其中以該穩定調配物之總重量計,該胺穩定劑係以約3%至約8% w/w之量存在。
19.如上述任何實施例之穩定調配物,其中以該穩定調配物之總重量計,該氮穩定劑組分係以約5%至約50% w/w之量存在。
20.如上述任何實施例之穩定調配物,其中該氮穩定劑組分包含以該穩定調配物之總重量計,以約5%至約15% w/w之量存在的脲酶抑制劑,及以該穩定調配物之總重量計,以約5%至約20% w/w之量存在的硝化抑制劑。
21.如上述任何實施例之穩定調配物,其中該氮穩定劑組分包含以約5%至約15% w/w之量存在的脲酶抑制劑;以約5%至約20% w/w之量存在的硝化抑制劑;以約50%至約75%之量存在的非質子性溶劑;及以約3%至約8% w/w之量存在的胺穩定劑,其中所有重量均以該穩定調配物之總重量計。
22.如實施例20或21之穩定調配物,其中該脲酶抑制劑為DCD且該硝化抑制劑為NBPT。
23.如實施例20至22中任一項之穩定調配物,其中該非質子性溶劑為DMSO。
24.如實施例20至23中任一項之穩定調配物,其中該胺穩定劑為單乙醇胺。
25.一種農業組合物,其包含如前述實施例中任一項之穩定調配物及肥料。
26.如實施例25之農業組合物,其中該肥料為含脲肥料。
27.如實施例25或26之農業組合物,其中該含脲肥料為糞肥。
28.如實施例25至27中任一項之農業組合物,其中該含脲肥料係以約1-12莫耳/L之位準存在。
29.如實施例25至28中任一項之農業組合物,其中該穩定調配物以水性分散液形式施用至該肥料之表面。
30.一種抑制土傳脲酶之方法,該方法包含以下步驟:將如前述實施例中任一項之穩定調配物施用至土壤,該調配物以足以抑制由土傳脲酶之作用引起的脲分解之量存在。
31.一種對土壤施肥之方法,其包含向該土壤施用如請求項1至24中任一項之穩定調配物或如實施例25至29中任一項之農業組合物。
32.一種用於製備如實施例1至24中任一項之穩定調配物之方法,其包含以下步驟:將有機酸酐組分與第一非質子性溶劑混合以形成有機酸酐組分預混合溶液;取出該有機酸酐組分預混合溶液之等分試樣;用第二非質子性溶劑稀釋所取出之等分試樣以得到有機酸酐溶液;使該有機酸酐溶液與胺穩定劑接觸以得到穩定有機酸酐溶液;及向該穩定有機酸酐溶液中添加氮穩定劑組分以得到所需穩定調配物。
33.如實施例32之方法,其中該第一及第二非質子性溶劑為DMSO。
34.如實施例32之方法,其中混合步驟在約70℃至約100℃範圍內之溫度下進行。
35.如實施例32至34中任一項之方法,其中以該有機酸酐組分預混合溶液之總重量計,該有機酸酐組分之量在約5%至約25% w/w範圍內。
36.如實施例32至35中任一項之方法,其中以該有機酸酐組分預混合溶液之總重量計,該有機酸酐組分預混合溶液之等分試樣之量在約25%至約50% w/w範圍內。
37.如實施例32至36中任一項之方法,其中以該穩定調配物之總重量計,胺穩定劑之量在約1至約20% w/w範圍內。
38.如實施例32至37中任一項之方法,其中該氮穩定劑組分包含脲酶抑制劑及硝化抑制劑。
39.如實施例38之方法,其中添加該氮穩定劑組分包含逐次添加該脲酶抑制劑及該硝化抑制劑。
40.如實施例39之方法,其中該硝化抑制劑係在該脲酶抑制劑之前添加。
41.如實施例40之方法,其中添加步驟進一步包含在添加該硝化抑制劑之後且在添加該脲酶抑制劑之前冷卻該穩定有機酸酐溶液。
實例
實例1:製備預混合聚合物溶液
製備含有80% w/w二甲亞碸(DMSO)(加熱至175℉(79℃))及20% w/w有機酸酐聚合物1之預混合聚合物溶液。首先,在不鏽鋼混合容器中將DMSO加熱至175℉(79℃)。混合預混合溶液直至全部聚合物完全溶解且觀測到澄清溶液為止。
視所製備之聚合物配方%而定,此預混合聚合物溶液可以視情況用額外DMSO溶劑稀釋。
實例2:製備5-20-5(聚合物1-DCD-NBPT)配方
將實例1中之25.0% w/w預混合聚合物溶液轉移至不鏽鋼加熱反應器中且將槽加熱至175℉(79℃)。在加熱時,向溶液中再添加額外45% w/w
DMSO。隨後,添加5% w/w單乙醇胺(MEA)。添加之後,偵測到顏色變化為更暗的黃色溶液。再持續混合反應混合物30分鐘。
將20% w/w DCD緩慢添加至加熱的摻合槽中。反應混合物持續混合60分鐘,且分析樣品以確保DCD已完全溶解。在DCD已溶解後,使溶液冷卻至100℉。
最後,將5% w/w NBPT添加至處於100℉(38℃)或更低之溶液中。產物在混合的情況下變成綠色。繼續混合直至獲得呈透明黃色半黏稠物質之製成品。
遵循以上程序以製備表1-3中所展示之調配物。
實例3:在無預混合聚合物溶液的情況下製備5-20-5(聚合物1-DCD-NBPT)配方
在不鏽鋼反應器中將65% w/w DMSO加熱至175℉(79℃)。將5% w/w乾燥聚合物緩慢篩分至溶液中。添加完成後,將反應混合物混合直至所有聚合物完全溶解且溶液變成淡黃色澄清外觀。添加5% w/w單乙醇胺且所得溶液變成更暗的黃色。再持續攪拌反應混合物30分鐘。
將20% w/w DCD緩慢添加至加熱的摻合槽中。添加完成後,將反應混合物混合60分鐘,且移出樣品並測試以確保所有DCD完全溶解。在DCD已溶解後,使溶液緩慢冷卻至100℉(38℃)。
將5% w/w NBPT添加至處於100℉(38℃)或更低之溶液中。產物在混合的情況下變成綠色,繼續混合直至最終產生黃色製成品。
實例4:配方5-5-15之實地研究
此外,使用式5-5-15進行實地研究。圖1展示實地研究之結果,其中用無脲、含脲肥料及具有如本文所揭示之調配物之含脲肥料(以調配物之總重量計,具有15% NBPT、5% DCD及5%有機酸酐聚合物6 w/w)處理玉米田地。15-5-5調配物之施用速率為每噸脲2L調配物。圖1展示用含脲肥料及調配
物5-5-15處理之玉米產生具有最多玉米粒的最佳玉米穗。
實例5:實地研究
對栽培旱作玉米之免耕系統下的區域進行實地研究。所培養之玉米為具有100mL/ha之Standak Top且植物密度為77,000植物/ha的玉米雜交AG 8088 VT PRO(高產量)。將以下三種調配物以三種不同速率(1、2及3L/m3)施用至田地:三份調配物(10-10-10;%聚合物-%DCD-%NBPT)
三份V調配物(5-5-15;%聚合物%-%DCD-%NBPT)
三份N調配物(5-20-5;%聚合物%-%DCD-%NBPT)
作為對照,植物僅用氮肥(例如,具有30%-45% N的UAN)處理或未經處理。
氮肥之施用量為135kg/ha的N,其對應於10.8噸/ha玉蜀黍的施用量為75N/bu。此外,採用典型的除草劑、殺真菌劑及殺昆蟲劑程式在整個研究期間去除因雜草、疾病或昆蟲所致之所有研究可變性;量測硝酸還原酶在V2-V3及開花(初次完全發育之葉片,每塊地三個植物)時之活性。此外,在施加蓋板之後高達30天進行土壤採集以測定N-NO3及N-NH4。此方法由Cataldo等人(1975)及Kemper;Zewers(1986)採用。土壤肥沃度中心(CEFERT)。每30天對乾植物質量進行生長分析。在生理成熟期進行收集。收集每塊地的三個中線之植物,每端不包括1.0公尺。量測列且對每列所收穫之植物及穗之數目進行計數。在收穫之後,進行手動剝離且測定100個穀粒質量以及作物產量。以kg/ha及bu/英畝為單位估測收穫結果。
a三份與以1L/m3速率施用之UAN肥料(30%-45% N)組合;b三份與以2L/m3速率施用之UAN肥料(30%-45% N)組合;c三份與以3L/m3速率施用之UAN肥料(30% N)組合;d與以1L/m3速率施用之UAN肥料(30%-45% N)組合的三份V;e與以2L/m3速率施用之UAN肥料(30%-45% N)組合的三份V;f與以3L/m3速率施用之UAN肥料(30%-45% N)組合的三份V;g與以1L/m3速率施用之UAN肥料(30%-45% N)組合的三份N;h與以2L/m3速率施用之UAN肥料(30%-45% N)組合的三份N;i與以3L/m3速率施用之UAN肥料(30%-45% N)組合的三份N;Anava:f,0.05;CV%:17.92%;Scott knott<0.1;1生產乾質量之玉米植物:葉片;2生產乾質量之玉米植物:玉米植物莖;3;4生產總乾質量之玉米植物;530天內第一次及第二次採集之土壤中的NO3值;630天內第一次及第二次採集之土壤中的NH4值;7葉片中之硝酸還原酶之酶活性;8葉氮含量。
收穫結果進一步展示於圖2中,相比於未經處理之植物,其展示作物產量增加至少50%,且相比於經UAN處理之植物,作物產量增加至少5%。此外,圖3展示相比於未經處理之穗,自經脲(@135kg/ha N)處理之玉蜀黍植物獲得的玉米穗展現更多玉米粒。圖4展示,相比於未經處理之玉米穗,經所揭示之調配物與氮肥組合處理之玉米穗展現增加的玉米穗中存在的玉米列的量。此進一步說明於圖5及圖6中,圖5比較所有三種處理之玉米穗軸,圖6比較經如本文所揭示之調配物與氮肥組合處理之玉米穗及未經處理的。
實例6:在美國不同地點的玉米帶進行實地研究。
在一般被稱作美國之玉米帶的不同美國地點進行實地研究,以便評估如本文所揭示之調配物與氮肥組合在各種土壤及氣候條件下對玉米生長及收穫的影響。
大量此等位置展現產量相對於對照提高(亦即,僅用氮肥處理植物)。
此外,注意到,在不同美國地點的玉米帶區中施用到各田地之氮肥之量顯著低於各地點中之大學推薦(參見表8)。不受理論束縛,但咸信由於所揭示之調配物中DCD(硝化抑制劑)及NBPT(脲酶抑制劑)之組合,使氮肥中存在之脲之轉化減至最小,且因此隨後使亞硝酸鹽/硝酸鹽之浸出及/或氨之揮發減至最小。此外,調配物中聚合物之存在促進養分至植物之可供使用性。因此,與本文所揭示之調配物一起採用的氮肥之量比推薦量小至少60%。
Claims (34)
- 一種穩定調配物,其包含氮穩定組合物、媒劑及胺穩定劑:其中以所述穩定調配物之總重量計,所述氮穩定組合物係以約5%至約50% w/w之量存在並包含氮穩定劑組分及有機酸酐組分,該氮穩定劑組分為脲酶抑制劑及/或硝化抑制劑,且所述有機酸酐組分為含有至少兩種不同重複單元的有機酸酐聚合物,其中所述至少兩種不同重複單元中之一者是衍生自經取代之烯烴、未經取代之烯烴或其組合的C型重複單元;其中以所述穩定調配物之總重量計,所述媒劑係以約50%至約75% w/w之量存在並包含非質子性溶劑;且其中以所述穩定調配物之總重量計,所述胺穩定劑係以約3%至約8% w/w之量存在。
- 如請求項1之穩定調配物,其中該氮穩定劑組分為N-(正丁基)硫代磷酸三醯胺(NBPT)及/或二氰胺(DCD)。
- 如請求項1之穩定調配物,其中該有機酸酐聚合物為無規共聚物。
- 如請求項1之穩定調配物,其中所述至少兩種不同重複單元中之一者是衍生自順丁烯二酸酐、伊康酸酐之(未)經取代之單體或其組合的B型重複單元。
- 如請求項1之穩定調配物,其中所述至少兩種不同重複單元中之一者是衍生自順丁烯二酸酐之經取代之單體、順丁烯二酸酐之未經取代之單體或其組合的B型重複單元。
- 如請求項4之穩定調配物,其中該有機酸酐聚合物之至少約50莫耳%之該等重複單元為B型重複單元。
- 如請求項1之穩定調配物,其中該烯烴係選自乙烯、丙烯、丁 烯、異丁烯、苯乙烯、甲基乙烯醚及其組合。
- 如請求項1之穩定調配物,其中該非質子性溶劑係選自二氯甲烷、二甲基乙醯胺、二甲基甲醯胺、二甲亞碸(DMSO)、乙酸乙酯、丙酮、乙腈、六甲基磷醯胺、二甲碸、環丁碸、1,3-二甲基-2-咪唑啶酮、1,3-二甲基-3,4,5,6-四氫-2(1 H)-嘧啶酮、乙酸甲酯、乳酸乙酯、N-甲基吡咯啶酮、四氫呋喃及碳酸伸丙酯。
- 如請求項9之穩定調配物,其中該非質子性溶劑為二甲亞碸(DMSO)。
- 如請求項1之穩定調配物,其中該胺穩定劑係選自1,2-二胺基環己烷(DCH)、雙(六亞甲基)三胺(BHT)、單乙醇胺、乙胺基乙醇、二甲胺基乙醇、異丙基胺基乙醇、二乙醇胺、三乙醇胺、甲胺基乙醇、胺基丙醇、甲胺基丙醇、二甲胺基丙醇、胺基丁醇、二甲胺基丁醇、胺基丁二醇、三羥甲胺 基乙烷、二乙胺基丙二醇、1-胺基-環戊烷甲醇及胺基苯甲醇。
- 如請求項10之穩定調配物,其中該胺穩定劑為單乙醇胺。
- 如請求項1之穩定調配物,其中該氮穩定劑組分包含以該穩定調配物之總重量計,以約5%至約15% w/w之量存在的脲酶抑制劑,及以該穩定調配物之總重量計,以約5%至約20% w/w之量存在的硝化抑制劑。
- 如請求項1之穩定調配物,其中該氮穩定劑組分包含以約5%至約15% w/w之量存在的脲酶抑制劑;以約5%至約20% w/w之量存在的硝化抑制劑;以約50%至約75% w/w之量存在的非質子性溶劑;及以約3%至約8% w/w之量存在的胺穩定劑,其中所有重量均以該穩定調配物之總重量計。
- 如請求項13之穩定調配物,其中該脲酶抑制劑為NBPT且該硝化抑制劑為DCD。
- 如請求項15之穩定調配物,其中該非質子性溶劑為DMSO。
- 如請求項16之穩定調配物,其中該胺穩定劑為單乙醇胺。
- 一種農業組合物,其包含如請求項1之穩定調配物及肥料。
- 如請求項18之農業組合物,其中該肥料為含脲肥料。
- 如請求項19之農業組合物,其中該含脲肥料為糞肥。
- 如請求項19之農業組合物,其中該含脲肥料係以約1-12莫耳/公升之含量存在。
- 如請求項19之農業組合物,其中該穩定調配物以水性分散液形式施用至該肥料之表面。
- 一種抑制土傳脲酶之方法,該方法包含以下步驟:將如請求項1之穩定調配物施用至土壤,該調配物以足以抑制由土傳脲酶之作用引起的脲分解之量存在。
- 一種對土壤施肥之方法,其包含向該土壤施用如請求項1之 穩定調配物。
- 一種用於製備如請求項1之穩定調配物之方法,其包含以下步驟:將有機酸酐組分與第一非質子性溶劑混合以形成有機酸酐組分預混合溶液;取出該有機酸酐組分預混合溶液之等分試樣;用第二非質子性溶劑稀釋所取出之等分試樣以得到有機酸酐溶液;使該有機酸酐溶液與胺穩定劑接觸以得到穩定有機酸酐溶液;及向該穩定有機酸酐溶液中添加氮穩定劑組分以得到所需穩定調配物。
- 如請求項25之方法,其中該第一及第二非質子性溶劑為DMSO。
- 如請求項25之方法,其中混合步驟在約70℃至約100℃範圍內之溫度下進行。
- 如請求項25之方法,其中以該有機酸酐組分預混合溶液之總重量計,該有機酸酐組分之量在約5%至約25% w/w範圍內。
- 如請求項25之方法,其中以該有機酸酐組分預混合溶液之總重量計,該有機酸酐組分預混合溶液之等分試樣之量在約25%至約50% w/w範圍內。
- 如請求項25之方法,其中以該穩定調配物之總重量計,胺穩定劑之量在約1至約20% w/w範圍內。
- 如請求項25之方法,其中該氮穩定劑組分包含脲酶抑制劑及硝化抑制劑。
- 如請求項31之方法,其中添加該氮穩定劑組分包含逐次添加該脲酶抑制劑及該硝化抑制劑。
- 如請求項32之方法,其中該硝化抑制劑係在該脲酶抑制劑之前添加。
- 如請求項33之方法,其中添加步驟進一步包含在添加該硝化抑制劑之後且在添加該脲酶抑制劑之前冷卻該穩定有機酸酐溶液。
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