TWI695826B - 製備除草羧酸鹽之方法 - Google Patents

製備除草羧酸鹽之方法 Download PDF

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TWI695826B
TWI695826B TW103137111A TW103137111A TWI695826B TW I695826 B TWI695826 B TW I695826B TW 103137111 A TW103137111 A TW 103137111A TW 103137111 A TW103137111 A TW 103137111A TW I695826 B TWI695826 B TW I695826B
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dicamba
carboxylic acid
water
sodium
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TW201516028A (zh
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詹姆士 布里斯托
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香港商龍燈農業化工國際有限公司
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Abstract

公開一種製備具有除草活性的羧酸鹽的方法，該方法包括以下步驟：i)將羧酸與高沸點、不與水混溶的有機溶劑混合，得到溶液或漿料；ii)在步驟(i)生成的溶液或漿料中加入一種鹼形成羧酸鹽；iii)除去步驟(ii)產生的混合物中的溶劑，得到羧酸鹽餅；及v)烘乾步驟(iii)得到的餅。
該方法尤其適合製備麥草畏(dicamba)鹽。一種製備麥草畏-鈉的方法包括：(1)將基本由麥草畏組成的羧酸溶解於高沸點、不與水混溶的惰性有機溶劑中，得到溶液或漿料；(2)在氫氧化鈉、碳酸氫鈉及彼等之混合物中選擇一種鹼，按照莫耳比1：0.97±0.6%加入步驟1的麥草畏溶液或漿料，形成麥草畏-鈉；(3)將步驟2中的反應混合物離心，得到麥草畏-鈉鹽餅；及(4)烘乾步驟3得到的麥草畏-鈉餅，得到乾燥的麥草畏-鈉，使其溶於水後的pH值始終介於7到10左右。

Description

製備除草羧酸鹽之方法
本發明關於一種製備有除草活性的羧酸鹽的方法
發明背景
人們發現，具有除草活性之羧酸，例如苯甲酸、苯氧羧酸、吡啶羧酸及喹啉羧酸，能控制在多種作物間生長的雜草。具體而言，這些羧酸被歸類為生長調節型除草劑，特點是通過合成激素作用抑制雜草在作物間生長。要控制雜草生長，則在雜草部位施加一種或以上有效除草劑量的此類羧酸除草劑，通常還會混合一種或以上農業可接受藥量的載劑、表面活性劑及其他助劑。
眾所周知，具有除草活性之羧酸以其酸類形式用於易感植物上，但是由於非水溶性酸類不能有效滲透易感植物的葉片，實現迅速有效地控制和根除雜草的目的，其除草效果不甚理想。因此，具有除草活性之羧酸通常由酸類轉化為脂類或鹽類，以增強其水溶性和葉片滲透性。脂類和鹽類的具有除草活性之羧酸都可在市場上購得。
製備羧酸鹽的常規方法是通過羧酸水溶液與含鹼金屬或銨的鹼 性溶液反應，產生對應的羧酸鹽和水。然後，一般將該羧酸鹽乾燥得到固體除草劑。
美國專利3,013,054描述了一種製備2-甲氧基-3,6-二氯苯甲酸鈉的方法，其中2-甲氧基-3,6-二氯苯甲酸(116克；0.5莫耳)溶於500毫升甲醇中，然後加入溶於100毫升甲醇的氫氧化鈉溶液(20克；0.5莫耳)。通過蒸氣浴在真空中蒸餾移除甲醇，將固體殘渣與100毫升冷乾醚混合成漿，然後過濾、乾壓(pressed dry)及在真空乾燥機中完全乾燥得到所需的鹽2-甲氧基-3,6-二氯苯甲酸鈉。
美國專利5,266,553描述了一種製備固體鹽的方法，其中將相應的芳氧羧酸與一種鹽中和，將產生的水溶液在控制條件下蒸發轉化成固體鹽。也可以通過將類似的市售芳氧基鹽溶液蒸發除水的方式製備固體鹽。
這些已知方法存在的其中一個問題是成本。具體而言，要乾燥形成的羧酸鹽必須加熱鹽溶液。由於在製備酸溶液時使用及在形成羧酸鹽時均產生了大量的水，因此就乾燥羧酸鹽溶液提供的所需熱能成本昂貴。
生產羧酸鹽的另一個相關問題是羧酸鹽溶液的pH值。現有多種方法來控制羧酸鹽溶液及得到的羧酸鹽pH值。具體而言，由於最終在使用時，得到的羧酸鹽通常被重新溶於水中，因此確保鹽溶於水中後得到合適的pH值很重要。控制羧酸鹽pH值的一種方法是在乾燥前中和該溶液。例如，羧酸鹽中混合鹼性化合物緩沖液來得到所需pH值的羧酸鹽溶液。
美國專利5,266,553描述了一種生產羧酸鹽的方法，其中從羧酸鹽及鹼性化合物中生成羧酸鹽，然後將羧酸鹽與第二種鹼性緩沖化 合物反應，生成一種溶解度增高的羧酸鹽。控制該鹽的pH值得另一種方法是製備不同批次的羧酸鹽，然後混合這些批次的羧酸鹽得到想要的pH值。然而，當這些鹽很粘稠及需要確保產品品質一致時，乾燥鹽的方法很困難。
產量和純度是已知方法中存在的另一個問題。先前技提供的方法只適用於實驗用途。然而，如果針對工業化生產，則尚未解決低產和低純度的問題。
因此，需要改進製備固體、自由流動及水溶性羧酸鹽的方法，尤其是需滿足工業化生產需求。
發明概述
本發明乃有關一種製備有除草活性的羧酸鹽的方法，該方法包括以下步驟：i)在高沸點及不與水混溶的有機溶劑中加入羧酸鹽，得到一種溶液或漿料；ii)將步驟(i)中產生的溶液或漿料與一種鹼反應，生成一種羧酸鹽；iii)將溶劑從步驟(ii)中產生的混合物中移除，得到羧酸鹽餅；及iv)乾燥步驟(iii)得到的餅。
本發明是一種適合製備固體、自由流動及可直接溶於水的具有除草活性之羧酸鹽的方法，尤其適用於工業化範疇。本方法因其耗能更低為特點，比已知生產具有除草活性之羧酸鹽之方法的成本更低。同時，本方法有利改善環境。
發明詳述
本發明是一種用於製備具有除草活性之羧酸的方法。本發明的方法可適用於任何具有羧酸特性的除草活性化合物。這些是該領域已知的具有除草活性之羧酸，可以在市場上買到。羧酸優選選自於苯甲酸、苯氧羧酸、吡啶羧酸及喹啉羧酸。
優選的苯甲酸除草劑為2-甲氧基-3，6-二氯苯甲酸(麥草畏)、3，5，6-三氯鄰甲氧基苯甲酸(殺草畏(tricamba))、3-胺基-2，5-二氯苯甲酸(滅草平)、5-2[2-氯-4-(三氟甲基)苯氧基]-2-硝基苯甲酸、2，3，5-三碘苯甲酸以及三氯苯甲酸。優選的苯氧基羧酸類除草劑為2，4-二氯苯氧基乙酸(2，4-D)、4-(2,4-二氯苯氧基)丁酸(2，4-DB)、2-(2，4-二氯苯氧基)丙酸(2，4-DP)、2，4，5-三氯苯氧基乙酸(2，4，5-T)、2-(2，4，5-三氯苯氧基)丙酸、4-氯-2-甲基苯氧基乙酸(MCPA)、2-(4-氯-2-甲基苯氧基)丙酸(MCPP)、4-(4-氯-2-甲基苯氧基)丁酸(MCPB)及2-[4-(2’，4’-二氯苯氧基)苯氧基]丙酸。優選的吡啶羧酸類除草劑包括4-胺基-3，5，6-三氯吡啶甲酸(毒莠定(picloram))、3，5，6-三氯-2-吡啶氧乙酸(綠草定(triclopyr))、二氯吡啶酸(clopyralid)及氟草煙(fluroxypyr)。優選的喹啉羧酸類除草劑包括二氯喹啉酸及喹草酸。
本發明方法特別適用於製備苯甲酸除草劑，尤其是麥草畏。
本發明的方法中使用了一種溶劑。該溶劑為高沸點、不與水混溶的有機溶劑。該溶劑基本上為惰性，即不會與羧酸或羧酸鹽反應。為通過規範的方式，有效從反應混合物及羧酸鹽中分離羧酸鹽，提高產量，優選的適合溶劑不能或只能對本方法中生產的羧酸鹽產生 微弱的溶劑化作用。
羧酸中加入該溶劑產生溶液或漿料。合適的溶劑包括任何可作為羧酸原料的溶劑及/或夾帶劑的溶劑。
該溶劑具有高沸點。高沸點溶劑通常指沸點超過70℃的溶劑。該溶劑的優選沸點為超過80℃。
合適有機溶劑包括芳烴溶劑(如甲苯和二甲苯)、濃度更高、不與水混溶的醇(如正丁醇和異丁醇)、戊醇、己醇、庚醇及彼等之混合物。
在該方法的一個具體實施方案中，上文所述的高沸點、不與水混溶的惰性有機溶液適用於溶解羧酸，並能有效溶解羧酸或使其達到良好的懸浮性。優選方案，羧酸鹽原料可溶於選定的有機溶劑，使用足夠的溶劑用於生成羧酸鹽溶液。
在優選具體實施方案中，上述高沸點、不與水混溶的有機溶劑作為夾帶劑使用，且適用於從反應混合物中除去水。鹼中可能出現水，例如所用的鹼呈是水溶液形態，及/或產生自羧酸鹽與該鹼之間的反應。具體而言，優選該有機溶劑與水生成共沸物。這樣可以通過共沸蒸餾脫去反應混合物中的水。
在該具體實施方案中，鹼中出現的水及/或在形成羧酸鹽時產生的水通過共沸蒸餾處理與高沸點、不與水混溶的惰性有機溶劑一起脫去。具體而言，當羧酸與鹼發生反應時可采用共沸蒸餾脫去反應混合物中的溶劑和水。共沸物的沸點由所選的溶劑決定。例如，二甲苯與水生成含60%二甲苯的共沸物，其沸點為94.5℃。甲苯與水生成含80%甲苯的共沸物，其沸點為85℃。
在一個具體實施方案中，所選溶劑使得溶劑/水共沸物的沸點高 於反應溫度。這樣可以在發生反應後從反應混合物中脫去溶劑。
如果反應溫度高於共沸物沸點，則該溶劑/水混合物可能通過蒸發處理從反應混合物中脫去。具體而言，羧酸和鹼反應釋放的熱量可用來蒸發溶劑/水共沸物。這樣，羧酸鹽和鹼反應產生的水可通過共沸物蒸發同時從反應物中脫去，例如反應混合物在反應發生時經過共沸蒸餾處理。在優選方案中，該選擇溶劑使得溶劑/水共沸物的沸點接近(+/- 5℃以內，更優選為+/- 3℃以內)或大致上與反應溫度相同。換言之，在優選方案中，該反應是在接近或達到溶劑/水共沸物的沸點時進行。
有機溶劑應優選對羧酸有較強溶劑化作用而對鹽有較弱溶劑化作用的溶劑，亦即，使羧酸易溶而使鹽難溶或基本不溶的溶劑。也可以選擇對雜質有較強溶劑化作用的溶劑，例如可能出現在羧酸原料中的氯酚、苯氧酸及其他有機雜質，即這些雜質易溶於該溶劑中。這樣，任何與鹼反應後的羧酸殘渣及任何雜質可以輕松地從鹽質中去除。
任何合適的鹼都可用來將羧酸轉變成相應的鹽。該鹼可以是有機或無機。優選的鹽為第I族或第II族金屬，例如鉀離子、鈉離子、鈣離子和鎂離子。第I族金屬鹼最優選鈉基鹼或鉀基鹼。含銨離子的鹼也非常適用於本發明方法。合適的有機鹼包括胺。
適合的鹼包括但不限於：鹼金屬氫氧化物，如氫氧化鈉和氫氧化鉀；鹼金屬氧化物；鹼金屬碳酸鹽及碳酸氫鹽，如碳酸鉀、碳酸鈉、碳酸氫鉀、碳酸氫鈉；鹼金屬醋酸鹽及甲酸，如醋酸鈉；氨；及碳原子數為1-4被烷氧基取代的伯胺、仲胺和叔胺，如乙醇胺及1,2-乙二胺。
如上文所指出，選擇恰當的有機溶劑能容易脫去反應混合物或反應產物中的水和溶劑。因此，可用液態溶液的鹼。
羧酸和鹼可在任何合適的溫度和氣壓條件下進行。合適的溫度範圍為50℃-250℃，優選50℃-200℃，更優選60℃-200℃，再優選60℃-150℃，再更優選80℃-150℃。在許多具體實施方案中，90℃-150℃範圍的溫度尤為適合。在正常或大氣壓下能最便捷地進行該反應。
可採用任何適宜的技術分離產生的羧酸鹽和有機溶劑。鑒於羧酸鹽在溶劑中的不溶性，因此優選用離心技術將鹽和溶劑分離。根據本發明製備的鹽可以通過常規乾燥方法進一步乾燥，例如在適合的溫度(如50℃-80℃)減壓進行接觸或對流乾燥法。
通常酸型除草化合物不與水混溶。因此，如果鹽裏出現一定量的酸型除草化合物，則除草劑鹽組成物不能完全溶於水。因此，常規的分離鹽方法包括在除草劑組成物中使用過量的鹼。過量使用鹼中和會提高組成物的pH值，而這可能導致腐蝕問題。若使用胺作為中和鹼，則組成物還會散發噁心的“魚腥”味。
出人意料地，實驗發現，按照本發明方法，羧酸並不一定要被鹼完全中和而得到基本可完全溶於水的具有除草活性羧酸鹽組成物。只要有97%以上的羧酸鹽被中和，便可分離出可溶於水的具有除草活性羧酸鹽。換言之，只需化學計量為97%以上的鹼與步驟(ii)的羧酸反應。因此，無需過量的鹼。所以，用本發明方法(例如用氨或氨的衍生物作為鹼)得到的產品腐蝕性更弱，氣味更淡。本發明方法中，優選在的莫耳百分數介於約97-100中使用足以中和羧酸原料量的鹼(變化值在1%以內，優選0.6%以內)。可通過該領域已知 的滴定法，來確定鹼的量和精確流速，以中和羧酸達到所需pH值範圍。
正如上文提到，本發明尤其適用與麥草畏一起使用。因此，在一個優選方案中，優選按莫耳比例1：0.97±0.6%(即1：0.964-1：0.976)混合麥草畏和鹼來製備麥草畏-鈉。鹼優選鹼金屬，特別是鈉基，例如選擇氫氧化鈉、碳酸氫鈉和他們的混合物。實驗發現，將麥草畏和鹼的比例控制在上述範圍內，可以產生溶於水後pH值穩定在7到10之間的麥草畏-鈉。
任何溶解或懸浮在高沸點、不混溶於水的有機溶劑中的羧酸鹽和任何殘留羧酸在步驟(iii)中被分離，例如通過離心機將羧酸鹽從有機溶劑中分離得到羧酸鹽餅。然後用乾燥機乾燥羧酸餅，除去殘留水分和溶劑。乾燥的羧酸鹽可回收為產品且無需緩沖劑或配料來調整pH值。
本發明方法能夠減少形成羧酸鹽而需要的熱能成本，從而減少羧酸鹽生產成本。高沸點、不與水混溶的惰性有機溶劑，特別是用共沸蒸餾法，可脫去製備鹼使用的水及/或羧酸鹽生成時產生的水，然後用溶劑分離。反應過程中產生的熱量可以直接用來蒸發共沸物。所有剩下的羧酸可通過離心機回收為羧酸餅。羧酸餅可添加進乾燥機，除去剩余的水和溶劑。因此，與已知方法相比，製備羧酸鹽整個流程中的加熱成本減少了。另外，反應過程中產生的水可用共沸蒸餾法脫去，這樣可以減少乾燥羧酸鹽所需的能量，從而帶來經濟效益。
此外，本發明方法可以生產更高產量和純度的羧酸鹽，特別是可以選擇高沸點、不與水混溶的惰性有機溶劑，因此對羧酸和雜質 溶劑作用較強，而對羧酸鹽溶劑作用較弱。
以下實例說明了本發明，但務請明白，本發明並不僅限於下列個別實例。
實例 實例一麥草畏-鈉的製備
用攪拌器將麥草畏(116克；0.5莫耳)溶解於1160克甲苯中。將碳酸氫鈉(19.3克，0.48莫耳)加入38.6毫升水中溶解成溶液，反應混合物回流反應2小時，反應溫度保持在甲苯/水共沸物的沸點。甲苯和水在反應過程中被蒸發，經歧管凝聚和收集。用離心機將形成的麥草畏鹽從冷卻後的反應混合物中分離形成餅。用真空烘箱乾燥餅得到溶於水後pH值為7的麥草畏-鈉。麥草畏-鈉鹽的產率為95%。
實例二二甲四氯-鉀的製備
用攪拌器將二甲四氯(20克；0.1莫耳)溶解於200克二甲苯中。溫度達到90℃-95℃時加入100毫升氫氧化鉀溶液(0.1M)，反應混合物回流反應2小時，反應溫度保持在甲苯/水共沸物的沸點。 二甲苯和水在反應過程中被蒸發，經歧管凝聚和收集。用離心機將形成的二甲四氯鹽從冷卻後的反應混合物中分離形成餅。用真空烘 箱乾燥餅，得到溶於水後pH值為9的二甲四氯-鉀。
實例三二氯吡啶酸(2-羥乙基)銨的製備
用攪拌器將二氯吡啶酸(192克；1莫耳)溶解於2000克正丁醇中。溫度達到85℃-90℃時加入61毫升乙醇胺(1莫耳)，反應混合物回流反應2小時，反應溫度保持在甲苯/水共沸物的沸點。正丁醇和水在反應過程中被蒸發，經歧管凝聚和收集。用離心機將形成的二氯吡啶酸從冷卻後的反應混合物中分離形成餅。用真空烘箱乾燥餅，得到溶於水後pH值為8的二氯吡啶酸(2-羥乙基)銨。二氯吡啶酸(2-羥乙基)銨的產率為96%。
實例四二氯喹啉酸-鈉的製備
用攪拌器將二氯喹啉酸(242克；1莫耳)溶解於2000克正丁醇中。溫度達到90℃-95℃時加入168毫升碳酸氫鈉(1M)。反應混合物回流反應2小時，反應溫度保持在甲苯/水共沸物的沸點。正己醇和水在反應過程中被蒸發，經歧管凝聚和收集。用離心機將形成的二氯喹啉酸鹽從冷卻後的反應混合物中分離形成餅。用真空烘箱乾燥餅，得到預期的鹽，即溶於水後pH值為10的二氯喹啉酸-鈉。二氯喹啉酸-鈉的產率為98%。

Claims (12)

  1. 一種製備具有除草活性之羧酸鹽的方法，該方法包括下述步驟：i)混合羧酸和高沸點、不與水混溶的有機溶劑得到溶液或漿料，其中溶劑的沸點至少為70℃，且溶劑與水形成共沸物；ii)在共沸物之沸點+/- 5℃內的溫度下，將步驟(i)產生的溶液或漿料與鹼反應形成羧酸鹽，其中使用97%至100%化學計量的鹼與羧酸反應；iii)除去步驟(ii)產生的混合物中的溶劑得到羧酸鹽餅；及iv)乾燥步驟(iii)得到的鹽餅；其中該羧酸係選自苯甲酸、苯氧羧酸、吡啶羧酸及喹啉羧酸；且其中溶劑係選自甲苯、二甲苯、正丁醇、戊醇、己醇、庚醇及彼等之混合物。
  2. 根據申請專利範圍第1項所述的方法，其中溶劑對羧酸鹽顯示較弱或基本沒有溶劑化作用。
  3. 根據申請專利範圍第1項所述的方法，其中羧酸可溶於溶劑中。
  4. 根據申請專利範圍第1項所述的方法，其中當步驟(ii)的羧酸與鹼發生反應時，步驟(iii)中的溶劑連同水被除去。
  5. 根據申請專利範圍第4項所述的方法，其中用共沸蒸餾方法除去溶劑和水。
  6. 根據申請專利範圍第4項所述的方法，其中共沸物的沸點低於或接近或基本等於步驟(ii)之反應溫度。
  7. 根據申請專利範圍第1項所述的方法，其中鹼為無機鹼。
  8. 根據申請專利範圍第1項所述的方法，其中鹼為有機鹼。
  9. 根據申請專利範圍第1項所述的方法，其中步驟(ii)中提供的鹼 為水性混合物或溶液。
  10. 根據申請專利範圍第1項所述的方法，其中步驟(ii)中的反應在50℃至200℃的溫度條件下進行。
  11. 根據申請專利範圍第1項所述的方法，其中溶劑在步驟(iii)中通過離心脫去。
  12. 一種製備麥草畏-鈉的方法，包括步驟：(1)將基本上由麥草畏組成的羧酸溶解於高沸點、不與水混溶的惰性有機溶劑，得到溶液或漿料，其中溶劑的沸點至少為70℃，且溶劑與水形成共沸物；(2)在共沸物之沸點+/- 5℃內的溫度下，從氫氧化鈉、碳酸氫鈉及彼等之混合物中選擇一種鹼，按照莫耳比1：0.97±0.6%加入步驟1中的麥草畏溶液或漿料中，形成麥草畏-鈉；(3)將步驟2中的反應混合物離心，得到麥草畏-鈉鹽餅；及(4)烘乾步驟3得到的麥草畏-鈉餅，得到乾燥的麥草畏-鈉，其溶於水後的pH值始終介於7到10左右；其中溶劑係選自甲苯、二甲苯、正丁醇、戊醇、己醇、庚醇及彼等之混合物。
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