CN103025701A - 除草性盐的制备方法 - Google Patents

除草性盐的制备方法 Download PDF

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CN103025701A
CN103025701A CN2011800247437A CN201180024743A CN103025701A CN 103025701 A CN103025701 A CN 103025701A CN 2011800247437 A CN2011800247437 A CN 2011800247437A CN 201180024743 A CN201180024743 A CN 201180024743A CN 103025701 A CN103025701 A CN 103025701A
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E·卡维特斯
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Abstract

本发明公开了一种通过使具有芳香族取代基的羧酸除草剂与胺反应来制备具有芳香族取代基的羧酸除草剂的固体胺盐的方法，所述方法包括：使在醚溶剂中的具有芳香族取代基的羧酸除草剂与胺反应以形成胺盐，并从所述醚溶剂反应混合物中收集作为沉淀物的具有芳香族取代基的羧酸除草剂的胺盐，其中，所述醚是包含至少一个伯脂肪族基团的二脂肪族醚。

Description

除草性盐的制备方法
技术领域
本发明涉及除草性羧酸盐的制备方法，特别是用胺中和性碱形成的除草性芳香族羧酸盐。
背景技术
诸如具有芳基取代基的羧酸除草剂和具有芳氧基取代基的酸除草剂等芳香族羧酸除草剂已经应用了多年。许多此类除草剂特别可用于选择性控制阔叶植被。这些芳香族羧酸通常会转化成酯形式或盐形式，来提高在适当溶剂中的溶解度。许多除草剂的酯和盐形式是可商购得的，并作为液体浓缩物(在使用前要用水稀释)或作为水溶液出售。酯形式通常可作为有机溶剂类乳化性浓缩物而获得。另一方面，盐是水溶性的，并可作为水溶液或固体而获得。
Champion等(美国专利5266553号)描述了一种干燥的水溶性盐组合物的制造方法，该方法涉及使用包含水作为主要成分的溶剂。该方法具有高能耗需求，为了减少盐产物的分解，需要复杂设备来在低温下除去水。一些盐类，特别是2,4-D二甲基胺(DMA)盐已经使用丙酮作为溶剂进行制备。在该方法中，将2,4-D溶于丙酮中，并使丙酮溶液用DMA饱和。2,4-D DMA盐在形成时沉淀，并可以通过过滤分离并进行干燥。
在诸如丙酮等溶剂中形成盐还具有明显的问题，即降低方法的效能和经济可行性。尽管盐不溶于丙酮，但水的存在将显著增大溶解度以至于多达10%的产物可能仍然被溶解。
丙酮中还形成了杂质。这些杂质包括必须从系统中清除的亚异丙基丙酮和双丙酮醇。这些杂质还减少了能够重复使用的溶剂的量。这将明显降低产物产率，并产生废物处理问题。结果，很难从废物流中分离出有用的材料，因而当原材料相对昂贵(如MCPP和麦草畏)时，该方法是不经济的。另外，将不能使用某些苯氧酸如MCPP，因为所得的盐(如MCPP/DMA)在丙酮中溶解度过大。
需要一种用于制备具有取代基的羧酸除草剂的盐的方法，所述方法中产率较高、使杂质的形成最小化并能够容易地分离出固体形式的产物。
发明内容
本发明提供了一种通过使具有芳香族取代基的羧酸除草剂与胺反应来制备具有芳香族取代基的羧酸除草剂的固体胺盐的方法，该方法包括：使在醚溶剂中的具有芳香族取代基的羧酸除草剂与胺反应以形成胺盐，并从所述醚溶剂反应混合物中收集作为沉淀物的具有芳香族取代基的羧酸除草剂的胺盐，其中，所述醚是包含至少一个伯脂肪族基团(primary aliphatic group)的二脂肪族醚(dialiphatic ether)。
优选的是，所述醚溶剂具有式R3OR1，其中：
R是伯烷基，如甲基、乙基和正丙基；
R1选自C3～C6烷基，优选选自由正丙基、异丙基、正丁基、异丁基、叔丁基和异戊基组成的组。
优选的醚的具体实例包括甲基叔丁基醚、乙基叔丁基醚、异丙基甲基醚和异戊基甲基醚。通常，优选的是R为甲基。最优选的醚是甲基叔丁基醚。最优选的醚的沸点不超过70℃，并且优选为40℃～70℃。
胺优选选自由氨、烷基胺、二烷基胺、三烷基胺、烷醇胺、二烷醇胺和三烷醇胺以及它们的混合物组成的组。
烷基胺和烷醇胺的烷基部分优选各自为C1～C4烷基，更优选为甲基、乙基或它们的混合物。因而，优选的胺为C1～C4烷基胺、二(C1～C4烷基)胺、三(C1～C4烷基)胺、C1～C4烷醇胺、二(C1～C4烷醇)胺和三(C1～C4烷醇)胺。更优选的胺选自由氨、二甲基胺、乙基胺、二乙基胺、三乙基胺、乙醇胺、二乙醇胺、三乙醇胺、单异丙基胺和二异丙基胺组成的组。
优选的芳香族羧酸除草剂包括(a)具有芳基取代基的羧酸除草剂和(b)芳氧基烷酸除草剂。
优选的芳基羧酸除草剂选自苯甲酸和吡啶酸(皮考啉酸)除草剂。优选的芳基羧酸除草剂选自由2-甲氧基-3,6-二氯苯甲酸(麦草畏(dicamba))、3,5,6-三氯邻茴香酸(杀草畏(tricamba))、1-萘乙酸、3-氨基-2,5-二氯苯甲酸(草灭平(amiben))、2,3,5-三碘苯甲酸、三氯苯甲酸和2,4,6-三氯苯基乙酸(伐草克(fenac))组成的组。
优选的皮考啉酸除草剂选自二氯皮考啉酸，特别是3,6-二氯皮考啉酸(毕克草(clopyralid))和4-氨基-3,5,6-三氯皮考啉酸(毒莠定(picloram))。
优选的芳氧基烷酸除草剂包括：吡啶氧基烷酸，如三氯吡啶氧基乙酸(乙氯草定(trichlopyr))；多核芳氧基烷酸，如2-萘氧基丙酸；以及苯氧基烷酸除草剂，如式II的除草剂：
Figure BDA00002426458900031
其中，X和X1独立地选自卤素(优选氯)和甲基；
X2为氢或氨基(优选氢)；
R2为氢或甲基；且
n为1、2或3。
还更优选的芳氧基烷酸选自由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)、(RS)-2-(2,4-二氯苯氧基)丙酸(滴丙酸(dichlorprop))、(R)-2-(2,4-二氯苯氧基)丙酸(滴丙酸P)、(±)-2-(2,4,5-三氯苯氧基)丙酸(涕丙酸(fenoprop))、4-氯-邻甲苯氧基-乙酸(MCPA)、4-(4-氯邻甲苯氧基)丁酸(MCPB)、(RS)-2-(4-氯-邻甲苯氧基)丙酸(氯丙酸(Mecoprop))、(R)-2-(4-氯-邻甲苯氧基)丁酸(氯丙酸P)和3,5,6-三氯-2-吡啶氧基乙酸(乙氯草定)组成的组。
用于本发明更优选的具有芳香族取代基的羧酸选自由2,4-D、2,4-DB、麦草畏、滴丙酸、滴丙酸P、涕丙酸、MCPA、MCPB、氯丙酸、氯丙酸P、乙氯草定和毒莠定组成的组。
使用根据本发明的特定的醚提供酸的高溶解度和胺盐产物的不溶性。另外，尽管许多工作者认为由于可能形成过氧化物，从事醚的工作具有危险性，但是我们发现，本发明的方法中使用的醚在反应中保持惰性，并避免了杂质积累。此外，醚可以通过低温(即小于约60℃)蒸发而可以容易地从反应产物中除去。
本发明的方法的一个显著优势在于，产物可以从醚中沉淀出并进行收集，并且回收利用母液以用作进一步制备胺盐产物的反应溶剂。我们发现，这种循环只能在先前使用如丙酮等溶剂时有限度地进行，因为这些溶剂趋于在废物流中聚集杂质。因此，使用本发明的方法，可以基本上排除对于如丙酮等溶剂所必需的从废物流中清除杂质的过程，因而减少了废物。
本发明的另一优势在于本方法的效能，以及醚的制备允许在本发明方法的过程中加入配制佐剂。这样能够消除或显著减少胺盐除草剂的混合和配制。
佐剂可以与试剂一起加入到反应混合物中，或者在反应过程中或反应后加入到反应混合物中。以这种方式使用的优选佐剂包括水分散性佐剂。可以加入到反应混合物中的配制添加剂的实例包括：螯合剂，如木质素磺酸钠、酪蛋白、乙二胺四乙酸(EDTA)及其盐、次氮基三乙酸(nitrilotracetic acid)及其盐、乙二胺二琥珀酸(EDDS)及其盐；以及一种或多种表面活性剂，如乙氧基化辛基酚、乙氧基化壬基酚、乙氧基化醇和乙氧基化醇/丙氧基化醇共聚物，从而有助于盐在水中溶解和/或有助于喷涂液在喷涂表面展开。
本发明的方法涉及在存在作为反应溶剂的特定醚下具有芳基取代基的羧酸除草剂与胺的反应。醚溶剂的所需体积取决于所关注的芳香族羧酸起始材料在所采用的反应条件下的溶解度。
反应优选在高于30℃的温度、更优选高于35℃的温度下进行。温度优选不超过70℃，并在环境条件下取决于醚溶剂的沸点。芳香族羧酸和胺之间的反应通常是放热的，因而无需加热便会发生温度的显著升高。
在许多情况中，例如使用MTBE溶剂时，放热足以将温度升高至溶剂的沸点以上，因而有利的是为反应容器配备回流冷凝器。芳香族酸优选与约等摩尔量的胺反应，虽然可能需要稍微过量以消除残留的酸或使其最小化。胺优选加入至芳香族酸在醚溶剂的搅拌混合物中。应理解的是，酸在反应开始时不必全部溶解在醚中，只要其在反应中设置的条件下能够逐渐地溶解并反应。事实上，我们发现在许多情况中，有利的是使用的浓度大于能够完全溶解所需的浓度，因为放热可以用来在反应条件下提供对较高浓度的完全溶解。这样能够将使用的溶剂最小化。
通过中和具有芳香族取代基的羧酸除草剂而形成的胺盐通常将作为沉淀物而快速形成。反应可以通过简单地将少量反应混合物加入到水中，并观察(a)是否形成了沉淀物和(b)测量溶液的pH来进行监测。在水相中未出现沉淀物或pH持续为至少8，表示反应已完成并存在过量的胺。
在反应过程中使得反应残余物的温度升高的情况下，优选将反应物冷却，或在收集沉淀物前冷却至环境温度。可以通过常规手段如过滤或通过离心来收集沉淀物。优选通过离心收集。所得的产物通常优选在不超过60℃的温度下进行干燥。
如上所述，本发明的一个优点在于收集过程的母液可以回收利用。优选的是，回收至少90%的母液，更优选的是，基本上回收利用全部的母液。
现将参照以下实施例来描述本发明。应理解的是，提供实施例的目的是为了描述本发明，他们绝不限制本发明的范围。
实施例
下述本发明的通用方法用于实施例1～5的过程中。
通用方法
实验设备和步骤
500ml圆底三颈烧瓶配备有搅拌器、汲取管(引入DMA用)和温度计。
烧瓶中充有300ml MTBE (或来自上一循环的MTBE母液)，向MTBE中加入苯氧酸(约80g)，并搅拌混合物。然后引入无水DMA，同时继续搅拌。在引入DMA的过程中，沉淀出盐。
通过将少量反应混合物加入到水中来监测反应。当混合物提供8的pH并保持在该pH时，认为反应完成。产物在不高于60℃下进行过滤干燥。母液由新鲜的MTBE构成，并准备用于下一批次。
实验结果
实施例1：MCPA/DMA盐
MCPA工业级由荷兰Nufarm提供。
终产物具有以下特征：
·含量检测：810g/kg(平均值)
·PH：5.5～6.5(3%水溶液)
母液中的MCPA含量<1%。产物的吸湿性极强。
实施例2：麦草畏/DMA盐
麦草畏工业级由Novataris提供。
终产物具有以下特征：
·含量检测：800g/kg(平均值)
·PH：5.5～6.5(3%水溶液)
母液中的麦草畏含量<1%。产物的吸湿性极强。
实施例3：MCPP/DMA盐
MCPP工业级由荷兰Nufarm提供。
终产物：
·含量检测：810g/kg(平均值)
·PH：5.8～6.3(3%水溶液)
母液中的MCPP含量<1%。产物的吸湿性极强。
注：该产物不能使用其他任何溶剂制得。
实施例4：2,4-DP/DMA盐
2,4-DP工业级由荷兰Nufarm提供。
终产物：
·含量检测：807g/kg(平均值)
·PH：5.8～6.5(3%水溶液)
母液中的2,4-DP含量<1%。产物不具有吸湿性。
实施例5：基于MCPA、MCPP和麦草畏的DMA盐原位形成阔叶灭草剂(weader)将MCPA、MCPP和麦草畏以1.8:8:1的质量比加入至TBME中。
加入REAX.83.A (木质素磺酸钠螯合剂)、2质量%的酸和1%的二钠盐形式的EDTA。
搅拌该混合物直至酸混合物完全溶解。引入DMA并沉淀出产物。过滤并干燥产物。产物通过了使用0℃的3WHO水的稳定性测试。在冰箱中24小时后，未观察到沉淀物。制备出5批次的回收母液，全部产物均通过了稳定性测试。
pH水平为5.5～6.5(3%水溶液)。
母液中的总酸含量<1%。制剂具有吸湿性。
实施例6和比较例A
使用以下原材料：
1.2,4-D(工业级)
2,4-D(工业级)由Nufarm Limited(Laverton)制造(袋编号6080)。
该批次具有以下组成(重量%)：
Figure BDA00002426458900061
2.由Nufarm WA(Kwinana)提供60升瓶的DMA(无水)。
3.由Aldrich提供MTBE (99%)。
4.由Westvaco Polychemicals department提供Morewet(REAX83A)。
5.由Ajax Chemicals提供EDTA(酸形式)。
本实施例比较了使用丙酮作为溶剂制备24-D/DMA盐(比较例A)和使用MTBE作为反应溶剂的本发明方法。
比较例A的过程
将DMA(807kg)泵入配备有搅拌器并容有2,4-D(4000kg)在回收利用的丙酮母液中的溶液的反应器中，以得到总体积为1200升。
将温度保持在约25℃～30℃，并形成沉淀物2,4-D二甲基胺盐。
在离心机中收集产物，并回收利用母液。据发现，由于母液中积累杂质的结果而必须清除一定比例的回收利用液，从而导致损失相当比例的产物。母液中存在的产物(约总产物的10%)还需要通过蒸馏来除去丙酮。
实施例6过程
将MTBE装入配备有顶部回流冷凝器和搅拌器的反应器中。加入苯氧酸、REAX83和EDTA。混合物搅拌15分钟～20分钟。加入无水DMA直至溶液达到并保持在pH大于8。在引入DMA的过程中，将反应温度升至MTBE的沸点(56℃)。在引入DMA的过程中发生产物沉淀。利用水将所得产物浆液冷却至25℃，并在离心机中收集湿滤饼状的沉淀物。在干燥机中干燥来自离心机的湿滤饼，同时将母液回收至反应器中用于下一批次。在反应器中加入新鲜的MTBE以补偿MTBE损失。
结论
下表1提供了醚方法和丙酮方法的比较。
表1
Figure BDA00002426458900081

Claims (22)

1.一种具有芳香族取代基的羧酸除草剂的固体胺盐的制备方法，所述方法通过使具有芳香族取代基的羧酸除草剂与胺反应来进行，所述方法包括：使在醚溶剂中的具有芳香族取代基的羧酸除草剂与胺反应以形成胺盐，并从所述醚溶剂反应混合物中收集作为沉淀物的所述具有芳香族取代基的羧酸除草剂的胺盐，其中，所述醚是包含至少一个伯脂肪族基团的二脂肪族醚。
2.如权利要求1所述的方法，其中，所述醚溶剂具有式ROR1，
其中，
R是伯C1～C4烷基；和
R1选自C3～C6烷基，优选选自正丙基、异丙基、正丁基、异丁基、叔丁基和异戊基。
3.如权利要求2所述的方法，其中，所述溶剂具有式CH3OR1，其中R1选自C3～C6烷基。
4.如前述权利要求中任一项所述的方法，其中，所述醚的沸点为40℃～70℃。
5.如前述权利要求中任一项所述的方法，其中，所述醚溶剂选自甲基叔丁基醚、乙基叔丁基醚、异丙基甲基醚和异戊基甲基醚中的至少一种。
6.如前述权利要求中任一项所述的方法，其中，所述胺包括选自由氨、烷基胺、二烷基胺、三烷基胺、烷醇胺、二烷醇胺和三烷醇胺组成的组中的至少一种。
7.如权利要求6所述的方法，其中，所述烷基胺、二烷基胺、三烷基胺、烷醇胺、二烷醇胺和三烷醇胺的烷基部分各自为C1～C4烷基。
8.如前述权利要求中任一项所述的方法，其中，所述胺包括选自由C1～C4烷基胺、二(C1～C4烷基)胺、三(C1～C4烷基)胺、C1～C4烷醇胺、二(C1～C4烷醇)胺和三(C1～C4烷醇)胺组成的组中至少一种。
9.如前述权利要求中任一项所述的方法，其中，所述具有芳香族取代基的羧酸除草剂选自由(a)具有芳基取代基的羧酸除草剂和(b)芳氧基烷酸除草剂组成的组。
10.如前述权利要求中任一项所述的方法，其中，所述芳基羧酸除草剂包括选自苯甲酸和吡啶酸(皮考啉酸)除草剂中的至少一种。
11.如前述权利要求中任一项所述的方法，其中，所述芳基羧酸除草剂包含选自由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)、1-萘乙酸、3-氨基-2,5-二氯苯甲酸(草灭平)、2,3,5-三碘苯甲酸、三氯苯甲酸和2,4,6-三氯苯基乙酸(伐草克)组成的组中的至少一种。
12.如权利要求10所述的方法，其中，优选的皮考啉酸除草剂选自二氯皮考啉酸，特别是3,6-二氯皮考啉酸(毕克草)和4-氨基-3,5,6-三氯皮考啉酸(毒莠定)。
13.如前述权利要求中任一项所述的方法，其中，所述芳基羧酸除草剂为包含选自由以下物质组成的组中的至少一种的芳氧基烷酸除草剂：吡啶氧基烷酸(优选选自三氯吡啶氧基乙酸(乙氯草定))；多核芳氧基烷酸(优选选自2-萘氧基丙酸)；以及苯氧基烷酸除草剂(优选具有式II：
Figure FDA00002426458800021
其中，X和X1独立地选自卤素(优选氯)和甲基；
X2为氢或氨基(优选氢)；
R2为氢或甲基；且
n为1、2或3)。
14.如前述权利要求中任一项所述的方法，其中，所述芳基羧酸除草剂为包含选自由以下物质组成的组中的至少一种的芳氧基烷酸：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)、(RS)-2-(2,4-二氯苯氧基)丙酸(滴丙酸)、(R)-2-(2,4-二氯苯氧基)丙酸(滴丙酸P)、(±)-2-(2,4,5-三氯苯氧基)丙酸(涕丙酸)、4-氯-邻甲苯氧基-乙酸(MCPA)、4-(4-氯-邻甲苯氧基)丁酸(MCPB)、(RS)-2-(4-氯-邻甲苯氧基)丙酸(氯丙酸)、(R)-2-(4-氯-邻甲苯氧基)丁酸(氯丙酸P)和3,5,6-三氯-2-吡啶氧基乙酸(乙氯草定)。
15.如前述权利要求中任一项所述的方法，其中，所述具有芳香族取代基的羧酸除草剂包含选自由2,4-D、2,4-DB、麦草畏、滴丙酸、滴丙酸P、涕丙酸、MCPA、MCPB、氯丙酸、氯丙酸P、乙氯草定和毒莠定组成的组中的至少一种。
16.如前述权利要求中任一项所述的方法，其中，所述产物从醚中沉淀出并进行收集，并且回收利用母液以用作进一步制备胺盐产物的反应溶剂。
17.如前述权利要求中任一项所述的方法，其中，在所述方法的过程中加入配制佐剂。
18.如权利要求16所述的方法，其中，至少一种佐剂与试剂一起加入到反应混合物中，或者在反应过程中或反应后加入到反应混合物中。
19.如权利要求16或17所述的方法，其中，所述佐剂包括选自由螯合剂、以及一种或多种表面活性剂组成的组中的至少一种，以有助于盐在水中溶解和/或有助于喷涂液在喷涂表面展开。
20.如前述权利要求中任一项所述的方法，其中，所述反应在35℃～70℃的温度下进行。
21.如前述权利要求中任一项所述的方法，其中，所述反应混合物包含的溶剂浓度小于室温能够完全溶解所需的溶剂浓度，且所述反应物在所述方法的过程中变得能够溶解。
22.如前述权利要求中任一项所述的方法，其中，所述沉淀物通过离心收集。
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US10011552B2 (en) 2013-10-30 2018-07-03 Rotam Agrochem International Company Limited Process for preparation of herbicidal carboxylic acid salts
CN110839632A (zh) * 2018-08-20 2020-02-28 四川利尔作物科学有限公司 一种除草组合物
CN111548264A (zh) * 2020-04-10 2020-08-18 岳晟 一种除草剂二甲胺盐及其制备方法

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AU2011256119A1 (en) 2012-06-21
US20130316907A1 (en) 2013-11-28
WO2011143690A1 (en) 2011-11-24
CA2799679C (en) 2018-03-06
US8962527B2 (en) 2015-02-24
AU2011256119B2 (en) 2013-01-24
AR082370A1 (es) 2012-12-05
PL222656B1 (pl) 2016-08-31
BR112012029397A2 (pt) 2016-07-26
PL402880A1 (pl) 2013-11-12
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MX2012013355A (es) 2013-02-11
CA2799679A1 (en) 2011-11-24

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