CN1578622A - 农药制剂 - Google Patents

农药制剂 Download PDF

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CN1578622A
CN1578622A CNA028215559A CN02821555A CN1578622A CN 1578622 A CN1578622 A CN 1578622A CN A028215559 A CNA028215559 A CN A028215559A CN 02821555 A CN02821555 A CN 02821555A CN 1578622 A CN1578622 A CN 1578622A
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CN1273017C (zh
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R·P·瓦林顿
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Syngenta Ltd
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    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

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Abstract

本发明涉及一种浓缩农药溶液，它含有一种或多种水不溶性农药(通常是0.5－50％ w/v)和木质素(木质素和农药合适的重量比是1∶10至1∶1)，所述农药和木质素溶解在水混溶性极性溶剂中，其中极性溶剂优选N－甲基吡咯烷酮。该溶液可特别用于稳定贮藏的某种嗜球果伞素杀菌剂的可溶浓缩物。

Description

农药制剂
本发明涉及农药制剂，更具体的是指水不溶性农药的浓缩溶液。本发明还涉及这些浓缩溶液的制备方法及其水稀释形式的应用。
一些农药在水中的溶解度很低，并且在水中化学结构稳定，它们在市场上的销售形式通常是水悬浮液浓缩物(SCs)，在田间使用时需要稀释。作为浓缩物保藏以及用水进一步稀释时，悬浮的农药活性成分必须保持较小的颗粒尺寸，以使其呈悬浮状态。因此通常需要将活性成分碾碎，这既费时又增加投入。即便如此，还是常出问题，悬浮液在长时间的贮藏中由于沉淀而导致浓缩，沉淀的颗粒难以重悬，有时活性成分在贮藏中颗粒的尺寸会增加。
一种可供选择的办法是将水不溶性活性成分溶解在水不混溶性溶剂，例如芳烃中，以形成可乳化的浓缩物(EC)。它可作为稳定溶液贮藏，使用时用水稀释形成小颗粒尺寸的乳状乳化液。那些不易溶解在常规水不溶性溶剂中的水不溶性农药可溶解在水混溶性溶剂中形成能稳定贮藏的可溶性浓缩物(SL)。这些农药用水稀释后会形成悬浮液。例如，WO92/10937中描述了这种可溶性浓缩物。这些SL是三组分制剂，制剂中一种固体水不溶性农药和一种分散剂溶解在一种水混溶性溶剂中。其中公开的分散剂包括烷化乙烯吡咯烷酮聚合物，环氧乙烷环氧丙烷/丙二醇缩合物，壬基酚环氧乙烷加合物和各种乙氧基化物。溶剂包括乙腈，α-丁内酯，二甲基酮，二甲基呋喃，二甲基亚砜，甲醇和N-甲基吡咯烷酮。
用水溶性溶剂溶解水溶解度较低的活性成份的缺点是它们在水中的稀释性能极差。这些活性成分经常会变成粗大晶粒而快速沉降，既会带来应用上的问题，例如堵塞喷洒滤器或者喷嘴，又会使农药的生物利用率降低或者反复不定。因此为了阻止沉降，或者更通常而言为了减缓沉降，必须将额外的乳化剂或者分散剂以通常1∶1的比例与活性成分一起加入，但是这种浓度的表面活性剂本身可能会产生植物毒性问题。
本发明提供一种浓缩农药溶液，它含有一种或者多种水不溶性农药和木质素，所述农药与木质素溶解在水混溶性极性溶剂中。
用于本发明溶液浓缩物的农药为水不溶性，可以是固体或液体，但是本发明优选在室温下呈固态的农药。通常它们在水中的溶解度不会超过0.2％w/v。它们还必须溶于所选用的水混溶性极性溶剂。
农药的用量通常是总溶液体积的0.5-50％w/v，更常见的是1-30％w/v，典型的是5-20％w/v。
农药包括除草剂，杀虫剂和杀菌剂。本发明特别适用于在水中溶解度不超过0.2％w/v的各种农药或其混合物。用于本发明的农药实例包括草萘胺，吡氟氯禾灵，炔草酯，甲基磺草酮(mesotrione)，氯氰菊酯，甲体氯氰菊酯，乙体氯氰菊酯，环唑醇，噁醚唑，己唑醇，戊菌唑，戊唑醇，腈嘧菌酯，啶氧菌酯(picoxystrobin)，亚胺菌，叉氨苯酰胺，啶氧菌酯，pyraclostrobin，肟菌酯(trifloxystrobin)，环丙嘧啶，瑞毒霉，mefenoxam，氟啶胺，氟噁菌，多效唑，涕必灵和喹氧灵。然而，本发明特别适用于杀菌剂，尤其适用于三唑杀菌剂和嗜球果伞素(strobilurin)杀菌剂以及杀菌剂的混合物，特别是嗜球果伞素杀菌剂的混合物，例如啶氧菌酯与诸如己唑醇或者环唑醇这样的三唑杀菌剂的混合物。特别有用的溶液浓缩物是由选自下述的杀菌剂制成：腈嘧菌酯，啶氧菌酯，戊唑醇，环唑醇，以及啶氧菌酯与环唑醇的混合物。
术语木质素是指木质素的游离酸形式，而不是木质素的碱金属盐，例如钠盐，或者木素磺酸盐。木质素是可变分子量的苯基丙烯聚合物，可从木浆工业中所用硫酸盐和苏打加工过程的废液中获得。这样得到的木质素称为碱性木质素，进一步可命名为硫酸盐(或牛皮浆)木质素或者苏打木质素。特别适用本发明的是Indulin AT(Indulin AT是一种商标名)，是由松木硫酸盐造纸黑液制成的高纯度木质素，呈自由流动的棕色粉末形式。
本发明溶液浓缩物中木质素的用量相对于农药的用量的合适比例是木质素与农药总量的重量比为1∶10至1∶1，通常1∶8至1∶2，优选1∶6至1∶4，典型为1∶5。
任何既能溶解农药又能溶解木质素的水混溶性极性溶剂都可用于本发明。合适的溶剂包括γ-丁内酯，四氢糠醇，N-甲基吡咯烷酮，二甲基亚砜，N，N-二甲基甲酰胺和乳酸乙酯。优选的溶剂是γ-丁内酯，四氢糠醇，特别优选的溶剂是N-甲基吡咯烷酮。还可使用极性溶剂的混合物，例如，N-甲基吡咯烷酮和聚(乙二醇)200的50∶50混合物。溶剂的用量要足够使总溶液达到100％w/v。
虽然不是必需，但溶液浓缩物还可包括其它添加剂，例如，聚合物稳定剂或者抗沉淀剂以提高稀释度。合适的聚合物稳定剂或者抗沉淀剂的例子包括水溶性聚合物和水不溶性聚合物，例如乙基纤维素，干酪素，羟基丙基纤维素，AvicelTM CL-611(以晶态纤维素为基础)，AgrimerTM VEMA AN-216(一种乙烯基醚马来酸酐共聚物，MW为55,000-80,000)，NU-FILM-PTM(聚1-p-薄荷烯)和KelzanTM(一种黄原酸胶)。这些添加剂的适当用量为不超过总制剂的0.5％w/v，例如0.1-0.4％w/v，通常是0.25％w/v，这取决于其在所用极性溶剂中的溶解度。例如，溶解在以N-甲基吡咯烷酮为基础的浓缩物中，AvicelTMCL-611和KelzanTM的最大用量大约是0.1％w/v。
本发明具体实施方案中提供的一种浓缩农药溶液含有：
(a)1-30％w/v，通常是5-30％w/v，典型是10-20％w/v的一种或者多种水不溶性农药，和
(b)与组分(a)的重量比为1∶10至1∶1，通常1∶8至1∶2，优选1∶6至1∶4，典型1∶5的木质素，并且(a)和(b)都溶解在
(c)水混溶性极性溶剂中，例如γ-丁内酯，四氢糠醇，乳酸乙酯，和优选的N-甲基吡咯烷酮。
在上述实施方式中，浓缩溶液可任选添加不超过0.5％w/v的其它添加剂，诸如乙基纤维素这样的稳定剂或者抗沉淀剂。
将农药，木质素和任选的稳定剂或者其它添加剂溶解在极性溶剂中，制备得到本发明的浓缩溶液。各种组分可以任意顺序添加到溶剂中。通常在室温下适度搅动或者搅拌就可以完成。为了帮助溶解，可以加热溶剂至例如高达50℃。
需要使用时，用水稀释浓缩溶液，通常将溶液加到搅拌的水中以得到农药的水分散体，其中可含有例如0.0001-1％w/v的农药。然后可以以喷洒或其它已知技术，将这些农药水溶液施用到需要处理的地点。
因此，在本发明进一步的具体实施方式中，提供了一种抵抗或者控制农业害虫的方法，该方法包括向害虫或者虫害地区施用有效杀虫剂量的通过将本发明浓缩农药溶液在水中分散所制备得到的水分散体。
本发明浓缩农药溶液的优点是用水稀释后能产生亚微米级(约0.4μm)的基本单分散的微粒，该微粒随后能至少保持24小时稳定。
本发明用下面的实施例作详细说明。实施例中用到了下面的缩略词：
ai＝活性成分                    SL＝可溶浓缩物
ppm＝百万分比                   w/v＝重量/体积
w/w＝重量/重量                  init＝初始
NMP＝N-甲基吡咯烷酮             GBL＝γ-丁内酯
DMSO＝二甲基亚砜                THFA＝四氢糠醇
PEG200＝聚(乙二醇)，平均分子量200
EL＝乳酸乙酯
实施例1
本实施例表明如何评价根据本发明制备的各种浓缩农药溶液用水稀释后的微粒尺寸。试验结果来自于多种本发明溶液。
分散体测试方法
用吸液管将2.5ml溶液浓缩物加入到含有97.5ml CIPAC标准硬水的带盖Crow容器中，以测试制剂在水中的分散特性。当最初几滴加到水中时，记录初始“bloom”，然后颠倒容器三次，记录分散体的均一性。24小时内每隔一定时间进行检查，以检测是否出现沉淀或者结晶。
使用Malvern Mastersizer S检测稀释初始和24小时后的微粒尺寸。仪器参数如下：
多分散模式                   提供的微粒尺寸值：
模糊度  2-4％                体积中值直径(volume median diameter)D(v，0.5)
泵速度  40％                 体积平均值直径(volume mean diameter)D[4，3]
搅拌速度20％                 小于1μm的百分数
超声波-0
所用的CIPAC标准硬水类型是CIPAC A和CIPAC C。它们具有以下特征：
CIPAC A：20ppm硬度；pH5.0-6.0；Ca2+∶Mg2+＝1∶1
CIPAC C：500ppm硬度；pH7.0-8.0；Ca2+∶Mg2+＝4∶1
(a)腈嘧菌酯可溶浓缩物
制备在NMP中含有10％w/v腈嘧菌酯和各种不同水平木质素的SL制剂，并测试它们的稀释液特性。下边表1和2显示了试验结果。
表1：CIPAC A水中腈嘧菌酯的稀释液
  Indulin AT％w/v               初始CIPAC A               24小时CIPAC A
  平均值   中值 ％＜1μm     平均值     中值    ％＜1μm
    1   9.71   0.44     85.69     0.39     0.37     100.00
    2   3.46   0.38     90.56     1.25     0.39     95.68
    3   0.40   0.38     100.00     0.39     0.37     100.00
    5   0.39   0.37     100.00     0.38     0.36     100.00
    10   2.77   0.38     76.31     4.51     0.41     70.43
表2：CIPAC C水中腈嘧菌酯的稀释液
  Indulin AT％w/v             初始CIPAC C                24小时CIPAC C
    平均值   中值   ％＜1μm     平均值     中值   ％＜1μm
    1     -   -     -     0.88     0.38     94.11
    2     1.39   0.37     88.05     0.53     0.39     96.58
    3     0.74   0.38     93.62     1.96     0.41     83.11
    5     1.33   0.40     87.76     85.44     0.61     64.38
    10     5.14   0.90     51.93     7.15     1.90     39.38
上述结果表明Indulin AT的浓度在约2-3％时为保持细小微粒尺寸的最佳浓度。
浓度为5-10％时，24小时后有絮凝出现，特别是在CIPAC C中，显示微粒尺寸的平均值有所增加，尺寸小于1μm的百分数则有所减少。
(b)啶氧菌酯可溶浓缩物
制备在NMP中的10％ w/v SL制剂，该制剂中含有1，2和5％ w/v木质素，并分析24小时后稀释液的微粒尺寸。试验结果如表3所示。
表3：啶氧菌酯的稀释液
  Indulin AT％w/v              CIPAC A                 CIPAC C
  平均值   中值   ％＜1μm     平均值     中值 ％＜1μm
    1   14.01   0.56     76.32     23.81     0.68   65.22
    2   1.69   0.51     84.29     1.11     0.52   81.21
    5   1.78   0.46     86.54     1.16     0.57   73.57
(c)戊唑醇可溶浓缩物
制备在NMP中的10％ w/v SL制剂，该制剂含有5％木质素。表4显示了24小时后稀释液的试验结果。
表4：戊唑醇稀释液
  Indulin AT％w/v             CIPAC A              CIPAC C
  平均值   中值 ％＜1μm  平均值   中值 ％＜1μm
    5   0.36   0.35   100.00  0.37   0.36   100.00
(d)环唑醇可溶浓缩物
制备在NMP中的10％w/v SL制剂，该制剂含有5％木质素。表5显示了得到的试验结果。
表5：环唑醇稀释液
  Indulin AT％w/v              CIPAC A               CIPAC C
  平均值   中值 ％＜1μm   平均值   中值 ％＜1μm
    5   14.41   0.35   78.90   14.22   0.33   82.39
(e)啶氧菌酯/环唑醇混合物的可溶浓缩物
制备含有12.5％w/v啶氧菌酯和5.0％w/v环唑醇以及8％w/v木质素的SL制剂。表6显示了24小时后稀释液的试验结果。
    Indulin AT％w/v                 CIPAC A
    平均值   中值     ％＜1μm
    8     3.50   0.46     80.33
实施例2
本实施例说明了可选择的极性溶剂在制备本发明浓缩溶液中的应用以及其它农药的应用。
以腈嘧菌酯，己唑醇，氯氰菊酯和甲基磺草酮作为活性成分，以NMP作为溶剂，制备含有10％w/w活性成分和4％w/w Indulin AT的SL制剂，。此外，用下述溶剂制备了腈嘧菌酯的类似制剂：GBL，DMSO，THFA，乳酸乙酯和50％NMP/50％PEG 200。
表7显示了按实施例1描述的方法测试这些制剂稀释液(CIPAC C水中含有2500ppm的活性成分)的试验结果。
表7：可选择的极性溶剂
  溶剂     不同时间(小时)的稀释液质量   筛保留数值(75μm)
  初始    0.5     1.0     2.0     3.0     6.0     24.0
  NMP     *     *     *     *     *     *     *     0
  GBL     *     *     *     *     *     *     *     0
  DMSO     *     *     *     *     *     *     *     0
  THFA     *     *     *     *     *     *     *     0
  EL     *     *     *     *     *     *     *     0
  NMP/PEG     *     *     *     *     *     *     *     0
*细小亚微米微粒悬浮液
上述试验结果表明所有活性成分和溶剂的结合物24小时后的稀释液效果都令人满意，各种细悬浮液都通过了75μm筛。

Claims (11)

1.一种浓缩农药溶液，它含有一种或者多种水不溶性农药和木质素，所述农药和木质素溶解在水混溶性极性溶剂中。
2.根据权利要求1的浓缩农药溶液，其中农药的用量为0.5-50％w/v。
3.根据权利要求1或者2的浓缩农药溶液，其中农药是嗜球果伞素杀菌剂或三唑杀菌剂或它们的混合物。
4.根据权利要求1或者2的浓缩农药溶液，其中农药是选自下述的杀菌剂：腈嘧菌酯，啶氧菌酯，戊唑醇，环唑醇，以及啶氧菌酯与环唑醇的混合物。
5.根据前述任一权利要求的浓缩农药溶液，其中木质素的用量是：木质素与农药的重量比为1∶10至1∶1。
6.根据前述任一权利要求的浓缩农药溶液，其中极性溶剂是选自：γ-丁内酯，四氢糠醇，乳酸乙酯或N-甲基吡咯烷酮。
7.根据前述任一权利要求的浓缩农药溶液，其中包含聚合物稳定剂或者抗沉淀剂。
8.根据权利要求7的浓缩农药溶液，其中聚合物稳定剂或者抗沉淀剂是乙基纤维素。
9.一种浓缩农药溶液，包含：
(a)1-30％w/v的一种或者多种水不溶性农药，和
(b)与组分(a)的重量比为1∶10至1∶1的木质素，并且(a)和(b)都溶解在水混溶性极性溶剂中。
10.根据权利要求9的浓缩农药溶液，其中含有至多0.5％w/v的另一种添加剂。
11.一种抵抗或者控制农业害虫的方法，其中包括向害虫或者虫害地区施用有效杀虫剂量的通过将本发明浓缩农药溶液分散在水中而制备得到的水分散体。
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CN115297725A (zh) * 2020-04-17 2022-11-04 陶氏环球技术有限责任公司 农业制剂

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