CN105705481B - 制备除草羧酸盐的方法 - Google Patents

制备除草羧酸盐的方法 Download PDF

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CN105705481B
CN105705481B CN201480060871.0A CN201480060871A CN105705481B CN 105705481 B CN105705481 B CN 105705481B CN 201480060871 A CN201480060871 A CN 201480060871A CN 105705481 B CN105705481 B CN 105705481B
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carboxylic acid
mediben
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CN105705481A (zh
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J·T·布里斯托
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Jiangsu Rotam Chemical Co Ltd
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Abstract

本发明公开了一种制备具有除草活性的羧酸盐的方法，该方法包括以下步骤：i)将羧酸与高沸点、与水不混溶的有机溶剂混合，得到溶液或浆料；ii)用碱处理步骤(i)产生的溶液或浆料，形成羧酸盐；iii)将溶剂从步骤(ii)产生的混合物中除去，得到羧酸盐饼；以及v)干燥步骤(iii)得到的饼。该方法尤其适合制备麦草畏的盐。一种制备麦草畏‑钠的方法包括：(1)将基本由麦草畏组成的羧酸溶解于高沸点、与水不混溶的惰性有机溶剂中，得到溶液或浆料；(2)用选自氢氧化钠、碳酸氢钠和它们的混合物的碱，按照摩尔比1:0.97±0.6％处理步骤1的麦草畏溶液或浆料，形成麦草畏‑钠；(3)将步骤2中的反应混合物离心，得到麦草畏‑钠盐饼；以及(4)干燥步骤3得到的麦草畏‑钠饼，得到干燥的麦草畏‑钠，其溶于水后的pH值始终介于约7到10之间。

Description

制备除草羧酸盐的方法
发明领域
本发明涉及一种制备具有除草活性的羧酸盐的方法
发明背景
人们发现，具有除草活性的羧酸，例如苯甲酸、苯氧基羧酸、吡啶羧酸和喹啉羧酸，可用于控制各种作物中杂草的生长。具体而言，这些羧酸被归类为生长调节型除草剂，作为合成生长素防止作物中杂草的生长。在用于控制不需要的植物生长中，向杂草场所施用除草有效量的一种或多种这些羧酸除草剂，通常这些羧酸除草剂与一种或多种农业上可接受的载剂、表面活性剂及其他添加剂一起施用。
已知具有除草活性的羧酸以其酸形式被施用于易感植物。但是，由于非水溶性酸形式不能有效渗透易感植物的叶片，实现迅速有效地控制和根除杂草的目的，其除草效果不甚理想。因此，具有除草活性的羧酸通常由酸形式转化为酯类或盐类，以增强其水溶性和叶片渗透性。这类具有除草活性的羧酸的酯形式和盐形式都可在市场上购得。
制备羧酸盐的常规方法是通过羧酸水溶液与含碱金属或铵的碱性溶液反应，产生对应的羧酸盐和水。然后，一般将该羧酸盐干燥得到固体除草剂。
美国专利3,013,054公开了一种制备2-甲氧基-3,6-二氯苯甲酸钠的方法。在所公开的方法中，2-甲氧基-3,6-二氯苯甲酸(116克；0.5摩尔)溶于500cc甲醇中，用溶于100cc甲醇的氢氧化钠溶液(20克；0.5摩尔)进行处理。通过蒸气浴在真空中蒸馏移除甲醇，将固体残渣与100cc冷干醚混合成浆，然后过滤、压干(pressed dry)及在真空干燥机中完全干燥得到所需的盐2-甲氧基-3,6-二氯苯甲酸钠。
美国专利5,266,553提出了一种制备固体盐的方法，其通过用碱中和相应的芳氧基羧酸，然后通过在受控条件下蒸发水将产生的水溶液转化成固体盐。也可以通过从相应的市售芳氧基盐溶液蒸发除水制备固体盐。
这些已知方法存在的其中一个问题是成本。具体而言，要在羧酸盐形成后对其进行干燥，必须加热盐溶液。由于在制备酸溶液时使用及在形成羧酸盐时均产生了大量的水，因此就干燥羧酸盐溶液提供的所需热能成本昂贵。
涉及羧酸盐生产的另一个问题是羧酸盐溶液的pH值。现有多种方法来控制羧酸盐溶液及得到的羧酸盐的pH值。具体而言，由于最终在使用时，得到的羧酸盐通常被重新溶于水中，因此确保盐溶于水中后得到合适的pH值很重要。控制羧酸盐pH值的一种方法是在干燥前按需要中和该溶液。例如，将缓冲液如碱性化合物与羧酸盐混合以产生所需pH值的羧酸盐溶液。
美国专利5,266,553描述了一种生产羧酸盐的方法，其通过由羧酸盐和碱性化合物形成羧酸盐，然后将羧酸盐与第二碱性缓冲化合物反应，生成具有增高的水溶解度的羧酸盐。控制该盐的pH值的另一种方法是制备不同批次的羧酸盐，然后混合这些批次的羧酸盐得到想要的pH值。然而，很难干燥盐(特别是当这些盐是粘性时)并产生一致的产品。
产量和纯度是已知方法中存在的另一个问题。现有技术提供的方法只适用于实验室规模。然而，针对工业化生产，决低产率和低纯度的问题尚未解决。
因此，需要一种改进的用于制备固体、自由流动且易于溶于水的羧酸盐的方法，尤其是适用于在工业规模上使用的方法。。
发明概述
依据本发明，提供一种制备具有除草活性的羧酸盐的方法，该方法包括以下步骤：
i)将羧酸与高沸点、与水不混溶的有机溶剂混合，得到溶液或浆料；
ii)用碱处理步骤(i)中产生的溶液或浆料，形成羧酸盐；
iii)将溶剂从步骤(ii)中产生的混合物中除去，得到羧酸盐饼；
以及
iv)干燥步骤(iii)中得到的饼。
本发明方法适用于制备固体、自由流动且易于溶于水的具有除草活性的羧酸盐，尤其适用于工业规模。本方法因其能量需求低，使得生产具有除草活性的羧酸盐的成本比已知的方法的成本更低。同时，本方法对环境更友好。
发明详述
本发明方法适用于具有除草活性的羧酸。本发明方法可适用于任何具有羧酸官能度的除草活性化合物。这些具有除草活性的羧酸在本领域是已知的，许多可以在市场上买到。羧酸优选选自于苯甲酸、苯氧基羧酸、吡啶羧酸和喹啉羧酸。
优选的苯甲酸除草剂为2-甲氧基-3，6-二氯苯甲酸(麦草畏)、3，5，6-三氯邻茴香酸(杀草畏(tricamba))、3-氨基-2，5-二氯苯甲酸(灭草平)、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。优选的苯氧基羧酸类除草剂为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。优选的吡啶羧酸类除草剂包括4-氨基-3，5，6-三氯吡啶甲酸(毒莠定(picloram))、3，5，6-三氯-2-吡啶氧基乙酸(绿草定(triclopyr))、二氯吡啶酸(clopyralid)及氟草烟(fluroxypyr)。优选的喹啉羧酸类除草剂选自二氯喹啉酸及喹草酸。
本发明方法特别适用于苯甲酸除草剂，尤其是麦草畏。
本发明的方法中使用了溶剂。该溶剂为高沸点、与水不混溶的有机溶剂。该溶剂基本上为惰性，即不会与羧酸或羧酸盐反应。为了通过常规方式有效地从反应混合物中分离羧酸盐，并实现较高的产量，合适的溶剂优选对本方法中生产的羧酸盐无溶剂化作用或仅表现出微弱的溶剂化作用。
溶剂与羧酸混合形成溶液或浆料。合适的溶剂包括可作为羧酸起始材料的溶剂及/或夹带剂的任何溶剂。
该溶剂具有高沸点。高沸点溶剂通常指沸点超过70℃的溶剂。该溶剂的沸点优选高于80℃。
合适的有机溶剂包括芳烃溶剂，例如甲苯和二甲苯，与水不混溶的高级醇，例如正丁醇和异丁醇、戊醇、己醇、庚醇和它们的混合物。
在该方法的一个实施方式中，上文所述的高沸点、与水不混溶的惰性有机溶液适用于溶解羧酸，并且有利地以至少使羧酸盐溶解或良好悬浮的量使用。优选地，羧酸盐起始材料可溶于选定的有机溶剂，使用足够的溶剂用于生成羧酸盐溶液。
在优选的实施方式中，上述高沸点、与水不混溶的惰性有机溶剂作为夹带剂使用，且适用于从反应混合物中除去水。碱中可能存在水，例如当碱是以水溶液形式采用时，和/或产生自该羧酸与该碱之间的反应。具体而言，优选该有机溶剂与水生成共沸物。这样可以通过共沸蒸馏除去反应混合物中的水。
在该实施方式中，碱中存在的水及/或在形成羧酸盐过程中产生的水通过共沸蒸馏处理与高沸点、与水不混溶的惰性有机溶剂一起除去。具体而言，当羧酸与碱发生反应时可对反应混合物进行共沸蒸馏除去溶剂和水。共沸物的沸点由所选的溶剂决定。例如，二甲苯与水生成含60％二甲苯的共沸物，其沸点为94.5℃。甲苯与水生成含80％甲苯的共沸物，其沸点为85℃。
在一个实施方式中，所选溶剂使得溶剂/水共沸物的沸点高于反应温度。这样可以在发生反应后从反应混合物中除去水和溶剂。
如果反应温度高于共沸物沸点，则可以通过蒸发从反应混合物中除去该溶剂/水混合物。具体而言，由于羧酸和碱反应而释放的热量可用来蒸发溶剂/水共沸物。这样，羧酸和碱反应产生的水可通过共沸物蒸发同时从反应混合物中除去，例如使反应混合物在反应发生时经受共沸蒸馏处理。在优选的实施方式中，对溶剂进行选择，使得溶剂/水共沸物的沸点接近反应温度，即，+/-5℃以内，更优选为+/-3℃以内，或大致上与反应温度相同。换言之，在优选的实施方式中，该反应是在接近或达到溶剂/水共沸物的沸点的温度进行。
有机溶剂应优选对羧酸有较强溶剂化作用而对盐有较弱溶剂化作用，亦即，使羧酸易于溶解于该溶剂而盐微溶于或基本不溶于该溶剂。也可以选择对羧酸起始材料中存在的杂质(例如氯酚、苯氧酸及其他有机杂质)有较强溶剂化作用的溶剂，即这些杂质易溶于该溶剂中。这样，任何与碱反应后的羧酸残渣及任何杂质可以轻松地从盐产品中去除。
任何合适的碱都可用来将羧酸转变成相应的盐。该碱可以是有机碱或无机碱。优选的碱为第I族或第II族金属，例如钾、钠、钙和镁的碱。第I族金属碱是特别优选的，尤其是钠或钾的碱。含铵离子的碱也特别适用于本发明方法。合适的有机碱包括胺。
适合的碱的例子包括但不限于：碱金属氢氧化物，如氢氧化钠和氢氧化钾；碱金属氧化物；碱金属碳酸盐及碳酸氢盐，如碳酸钾、碳酸钠、碳酸氢钾、碳酸氢钠；碱金属乙酸盐及甲酸盐，如乙酸钠；氨；及碳原子数为1-4的烷基取代的伯胺、仲胺和叔胺，如乙醇胺和1,2-乙二胺。
如上文所指出，选择恰当的有机溶剂能容易将反应混合物或反应产物中的水与溶剂一起除去。因此，可用水溶液形式的碱。
羧酸和碱的反应可在任何合适的温度和压力条件下进行。合适的温度范围为50℃-250℃，优选50℃-200℃，更优选60℃-200℃，再优选60℃-150℃，再更优选80℃-150℃。在许多实施方式中，90℃-150℃范围的温度尤为适合。在常压或大气压下能最便捷地进行该反应。
可采用任何适宜的技术分离形成的羧酸盐和有机溶剂。鉴于羧酸盐在溶剂中的不溶性，因此优选通过离心将盐和溶剂分离。根据本发明制备的盐可以通过常规干燥方法进一步干燥，例如在适合的温度(如50℃-80℃)减压进行接触或对流干燥法。
通常酸型除草化合物不与水混溶。因此，如果盐里出现足够量的酸型除草化合物，则除草盐组合物不能完全溶于水。因此，常规的分离盐的方法包括在除草组合物中使用过量的碱。过量的中和碱会导致组合物具有高pH值，而这可能导致腐蚀问题。若使用胺作为中和碱，则组合物还会散发恶心的“鱼腥”味。
出人意料地，已经发现，按照本发明方法，羧酸并不一定要被碱完全中和而得到基本可完全溶于水的具有除草活性的羧酸盐组合物。只要有至少97％的羧酸盐被中和，便可分离出可溶于水的具有除草活性的羧酸盐。换言之，在步骤(ii)中需要提供的碱的量只需要是与羧酸反应所需的化学计量的97％以上即可。因此，无需过量的碱。所以，用本发明方法得到的产品腐蚀性更弱，气味更淡(例如用氨或氨的衍生物作为碱时)。本发明方法中，碱的用量优选为足以中和羧酸起始材料的量的约97-100摩尔％(变化值在约1％以内，优选0.6％以内)。可通过本领域已知的滴定法来确定碱的量和精确流速，以中和羧酸达到所需pH值范围。
正如上文提到，本发明方法尤其适用与麦草畏一起使用。因此，在一个优选实施方式中，优选按摩尔比例1:0.97±0.6％(即1:0.964-1:0.976)混合麦草畏和碱来制备麦草畏-钠。碱优选是碱金属碱，特别是钠碱，例如选自氢氧化钠、碳酸氢钠和它们的混合物。已经发现，将麦草畏和碱的比例控制在上述范围内，可以产生溶于水后pH值始终介于约7到10之间的麦草畏-钠。
羧酸盐和溶解或悬浮在高沸点、与水不混溶的有机溶剂中的任何残留羧酸在步骤(iii)中被分离，例如通过离心机分离，在此将羧酸盐从有机溶液中分离得到羧酸盐饼。然后用干燥机干燥羧酸盐饼，除去任何残留水分和溶剂。干燥的羧酸盐可回收为产品且无需缓冲剂或批料混合来调整其pH值。
由于减少形成羧酸盐而需要的热能成本，通过本发明方法制备的羧酸盐能够以较低的成本生产。制备碱使用的水和/或羧酸盐形成过程中产生的水可与高沸点、与不水混溶的惰性有机溶剂一起除去，特别是用共沸蒸馏法，然后与溶剂分离。反应过程中释放的热量可以直接用来蒸发共沸物。可通过离心从任何残留的羧酸中回收羧酸盐饼。羧酸盐饼可添加进干燥机，在此除去剩余的水和溶剂。因此，与已知方法相比，制备羧酸盐整个流程中的加热成本减少了。另外，反应过程中产生的水可用共沸蒸馏法除去，这样可以减少干燥羧酸盐所需的能量，从而带来经济效益。
此外，本发明方法可以生产更高产量和纯度的羧酸盐，特别是因为可以选择高沸点、与水不混溶的惰性有机溶剂，因此对羧酸和杂质的溶剂化作用较强，而对羧酸盐的溶剂化作用较弱。
以下实施例说明了本发明。但是应理解，本发明并不仅限于下列个别实施例。
实施例
实施例1麦草畏-钠的制备
在混合器中将麦草畏(116克；0.5摩尔)溶解于1160克甲苯中。添加氢氧化钠(19.3克，0.48摩尔)的水(38.6毫升)溶液，反应混合物回流反应2小时，反应温度保持在甲苯/水共沸物的沸点。甲苯和水在反应过程中被蒸发，冷凝，经歧管收集。然后通过离心将形成的麦草畏盐从冷却后的反应混合物中分离形成饼。用真空烘箱干燥饼得到溶于水后pH值为7的麦草畏-钠。麦草畏-钠盐的产率为95％。
实施例2MCPA-钾的制备
在混合器中将MCPA(20克；0.1摩尔)溶解于200克二甲苯中。在90℃-95℃添加100毫升氢氧化钾溶液(0.1M)，反应混合物回流反应2小时，反应温度保持在甲苯/水共沸物的沸点。二甲苯和水在反应过程中被蒸发，冷凝，经歧管收集。然后通过离心将形成的MCPA盐从冷却后的反应混合物中分离形成饼。用真空烘箱干燥饼，得到溶于水后pH值为9的所需盐MCPA-钾。
实施例3二氯吡啶酸-二(2-羟乙基)铵的制备
在混合器中将二氯吡啶酸(192克；1摩尔)溶解于2000克正丁醇中。在85℃-90℃添加61毫升乙醇胺(1摩尔)，反应混合物回流反应2小时，反应温度保持在甲苯/水共沸物的沸点。正丁醇和水在反应过程中被蒸发，冷凝，经歧管收集。然后通过离心将形成的二氯吡啶酸盐从冷却的反应混合物中分离形成饼。用真空烘箱干燥饼，得到溶于水后pH值为8的所需盐二氯吡啶酸-二(2-羟乙基)铵。二氯吡啶酸-二(2-羟乙基)铵的产率为96％。
实施例4二氯喹啉酸-钠的制备
在混合器中将二氯喹啉酸(242克；1摩尔)溶解于2000克正己醇中。在90℃-95℃添加168毫升碳酸氢钠(1M)。反应混合物回流反应2小时，反应温度保持在甲苯/水共沸物的沸点。正己醇和水在反应过程中被蒸发，冷凝，经歧管收集。通过离心将形成的二氯喹啉酸盐从冷却的反应混合物中分离形成饼。用真空烘箱干燥饼，得到所需的盐，溶于水后pH值为10的二氯喹啉酸-钠。二氯喹啉酸-钠的产率为98％。

Claims (19)

1.一种制备具有除草活性的羧酸盐的方法，所述方法包括以下步骤：
i)将羧酸与沸点高于70℃、与水不混溶的有机溶剂混合，得到溶液或浆料，其中所述溶剂与水形成共沸物，其中溶剂选自甲苯、二甲苯、正丁醇、和正己醇；
ii)用碱处理步骤(i)产生的溶液或浆料，形成羧酸盐，所述处理在接近所述共沸物的沸点的温度进行，所述溶剂/水共沸物的沸点在反应温度的+/-5℃以内；
iii)将溶剂从步骤(ii)产生的混合物中除去，得到羧酸盐饼；以及
iv)干燥步骤(iii)中得到的饼；
其中步骤(ii)中提供的碱的量为与羧酸反应所需的化学计量量的97％至100％。
2.如权利要求1所述的方法，其中所述羧酸选自苯甲酸、苯氧基羧酸、吡啶羧酸和喹啉羧酸。
3.如权利要求2所述的方法，其中所述羧酸选自下组：麦草畏、杀草畏、2,4-D、MCPA、毒莠定、二氯吡啶酸和二氯喹啉酸。
4.如权利要求3所述的方法，其中所述羧酸为麦草畏。
5.如权利要求1或2所述的方法，其中所述溶剂对羧酸盐显示较弱的溶剂化作用或没有溶剂化作用。
6.如权利要求1或2所述的方法，其中羧酸可溶于溶剂中。
7.如权利要求1所述的方法，其中在步骤(ii)的羧酸与碱发生反应的同时，在步骤(iii)中溶剂与水一同被除去。
8.如权利要求7所述的方法，其中通过共沸蒸馏除去溶剂和水。
9.如权利要求7或8所述的方法，其中共沸物的沸点低于步骤(ii)的反应温度。
10.如权利要求7或8所述的方法，其中共沸物的沸点等于步骤(ii)的反应温度。
11.如权利要求1或2所述的方法，其中碱为无机碱。
12.如权利要求11所述的方法，其中碱为第I族或第II族金属的碱或铵化合物。
13.如权利要求12所述的方法，其中所述碱选自碱金属氢氧化物、碱金属氧化物、碱金属碳酸盐、碱金属碳酸氢盐、碱金属乙酸盐、碱金属甲酸盐和氨。
14.如权利要求1或2所述的方法，其中碱为有机碱。
15.如权利要求14所述的方法，其中碱为具有1-4个碳原子的烷基取代的伯胺、仲胺和叔胺。
16.如权利要求1或2所述的方法，其中步骤(ii)中提供的碱为水性混合物或溶液。
17.如权利要求1或2所述的方法，其中步骤(ii)中的反应在50℃至200℃的温度下进行。
18.如权利要求1或2所述的方法，其中在步骤(iii)中通过离心除去溶剂。
19.一种制备麦草畏-钠的方法，该方法包括以下步骤：
(1)将由麦草畏组成的羧酸溶解于沸点高于70℃、与水不混溶的惰性有机溶剂中，得到溶液或浆料，其中所述溶剂与水形成共沸物，其中所述溶剂选自甲苯、二甲苯、正丁醇、和正己醇；
(2)用选自氢氧化钠、碳酸氢钠和它们的混合物的碱，按照麦草畏和碱的摩尔比为1:0.97±0.6％处理步骤1中的麦草畏溶液或浆料，形成麦草畏-钠，所述处理在接近所述共沸物的沸点的温度进行，所述溶剂/水共沸物的沸点在反应温度的+/-5℃以内；
(3)将步骤2中的反应混合物离心，得到麦草畏-钠饼；
(4)干燥步骤3中得到的麦草畏-钠饼，得到干燥的麦草畏-钠，其溶于水后的pH值始终介于7到10之间。
CN201480060871.0A 2013-10-30 2014-06-19 制备除草羧酸盐的方法 Expired - Fee Related CN105705481B (zh)

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