CN1826055A - 草甘膦的高强度、低粘度除草制剂 - Google Patents
草甘膦的高强度、低粘度除草制剂 Download PDFInfo
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及含有高浓度草甘膦一甲胺或二甲胺盐和一种或多种用以增强草甘膦盐除草活性的表面活性剂的高强度除草制剂。所述制剂在高浓度下具有明显较低的粘度。
Description
技术领域
本发明涉及N-膦酰基甲基甘氨酸(草甘膦)的高强度液体制剂,更特别地,涉及草甘膦的一甲胺(MMA)和二甲胺(DMA)盐的高强度液体制剂。
背景技术
草甘膦是一种已知的有效除草剂。美国专利4,405,531公开了许多可用作除草剂的草甘膦有机铵盐,包括甲胺盐和二甲胺盐,作为例子,一烷基铵和二烷基铵是特别优选的盐。目前市场上销售多种制剂,其中许多是可原样使用或在使用之前稀释的水溶液。典型地,草甘膦是以盐的形式提供,其表现出足够高的水溶性以提供高强度除草制剂。例如,美国专利6,277,788公开了草甘膦的异丙胺盐(IPA)和单乙醇胺(MEA)盐。此外,美国专利6,365,551和WO 01/89302公开了包含草甘膦的钾(K)盐的各种制剂。基于各种经济和环境因素,高强度制剂是合意的。例如,希望能提供高强度制剂以降低船运和操作成本以及减少必须弃置的包装材料的用量。高强度制剂应该在储存和船运过程中稳定并保持效力。此外,高强度制剂应该是在至少50℃的温度下稳定并在低至0℃的温度下不会有任何沉淀的澄清均质液体。
除草制剂通常含有增效表面活性剂。表面活性剂的加入是非常合意的,因为所得制剂表现出充分提高的除草活性。例如,WO 03/063589,描述了结合使用烷基甜菜碱表面活性剂和其它表面活性剂的草甘膦制剂。然而,所选表面活性剂或者与草甘膦盐互相反应,这提高了除草制剂的粘度,或者通常与草甘膦盐溶液不相容。某些表面活性剂,例如,氧化烯烷基胺类化合物中的一些表面活性剂与草甘膦盐结合时,会提高制剂的粘度。如果粘度过高,对浓缩的除草剂的操作就会变得困难。此外,对于施用到植物上或者稀释成浓度较低的喷雾液来说,高粘度液体难以精确测量。根据浓度和特定的表面活性剂,除草制剂可能形成凝胶,这使得多数施用都相当困难,甚至不可能进行。
常用的草甘膦IPA盐的制剂在浓度高于350克酸当量/升(gae/l),特别是在浓度高于440gae/l时,会变得越来越粘。高粘度使得制剂难以测量并难以用泵抽吸,在一季(the season)初期通常遇到的低温下尤为如此。
草甘膦的MEA和K盐的主要限制在于其与许多表面活性剂的不相容性。具体而言,美国专利6,277,788公开了聚氧乙烯烷基胺只有在碳原子总平均数加上氧化乙烯基团平均数的总和等于或小于25时才与草甘膦的MEA盐相容。尽管草甘膦的K盐具有形成低粘度、高强度草甘膦制剂的能力,但其具有一些明显限制,即许多常用于增强草甘膦效力的表面活性剂与草甘膦K盐溶液不相容。例如,常用的烷基胺乙氧基化物表面活性剂只有在乙氧基化程度不超过5时才相容(形成均质混合物)。然而,与乙氧基化程度较高(例如15-20摩尔环氧乙烷)的烷基胺乙氧基化物表面活性剂相比,低乙氧基化程度的烷基胺乙氧基化物表面活性剂造成眼刺激的可能性较高。
考虑到上述问题,相关领域仍然需要更大的改进,包括具有低粘度并含有适当有效的表面活性剂的改进的高强度除草制剂。本发明针对这些需要并提供了许多益处和优点。
发明内容
现在已经发现,草甘膦的一甲胺(MMA)和二甲胺(DMA)盐可以制备粘度极低的高强度液体制剂。此外,可以在该高强度制剂中加入足量的一种或多种增效表面活性剂,同时仍保持低粘度特征。本发明提供了一种高强度除草浓缩组合物,所述组合物含有:(a)水,(b)草甘膦,主要是MMA或DMA盐形式,以每升组合物高于350克酸当量(gae/l)的量溶于水,和(c)总量为每升组合物20至200克(g/l)的至少一种表面活性剂。
除草制剂包含一种对除草有效的表面活性剂。选择该表面活性剂以提高制剂的除草活性和使高强度制剂的粘度最小化。草甘膦的MMA和DMA盐与多种表面活性剂相容。优选的表面活性剂选自下列表面活性剂:
(a)具有下列化学通式的烷基胺和烷基醚胺表面活性剂
其中R1是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,R2和R3独立地为C1-C4烷基,优选为甲基,或总共含有2至22个烯化氧单元,优选为环氧乙烷单元的聚氧化烯链;
(b)具有下列化学通式的季铵表面活性剂
其中Z-是农业上可接受的阴离子,例如氯根、溴根、碘根、硫酸根或乙酸根,R4、R5、R6和R7包括,但不限于下面所述:
(i)R4是苄基或C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,且R5、R6和R7独立地为C1-C4烷基,优选甲基;
(ii)R4和R5独立地为C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,且R6和R7独立地为C1-C4烷基,优选甲基;
(iii)R4是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,R5是含有2至22个,优选2至15个C2-C4烯化氧单元(优选环氧乙烷单元)的聚氧化烯链,且R6和R7独立地为C1-C4烷基,优选甲基;或
(iv)R4是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,R5和R6是含有2至22个,优选2至15个C2-C4烯化氧单元(优选环氧乙烷单元)的聚氧化烯链,且R7是C1-C4烷基,优选甲基;
(c)具有下列化学通式的两性表面活性剂
R8R9R10N+-(CH2)nCOO-
其中R8、R9、R10和n包括但不限于如下所述:
(v)R8是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,且R9和R10独立地为C1-C4烷基,优选为甲基,或氢原子;n是1至5的整数;或
(vi)R8是[R11-CONH-(CH2)x-]基团,其中R11是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,x是1至5的整数,且R9和R10独立地为C1-C4烷基,优选甲基,或氢原子;n是1至5的整数;
(d)具有下列化学通式的脂肪醇乙氧基化物
R12-O-(CH2-CHR13-O)n-R14
其中通式R12是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,R13独立地表示氢原子或甲基或乙基基团,优选氢原子,n是2至50,优选10至30的整数,且R14是C1-C4烷基,优选甲基,或氢原子;
(e)具有下列化学通式的脂肪醇乙氧基化物磷酸酯
[R15-O-(CH2-CHR16-O)n]3-m-P(=O)(OM)m
其中通式R15是C6-C20,优选C8-C18,直链或支链、饱和或不饱和烃基,R16独立地表示氢原子或甲基或乙基基团,优选为氢原子,n是0至10,优选2至10的整数,M独立地表示氢原子、碱金属或碱土金属、铵或烷基铵离子,且m是1至2的整数;
(f)具有下列化学通式的烷基聚苷
其中聚苷是由葡萄糖或其它单-、二-或多糖衍生成的,n是聚合度且通常在1至3的范围内,R17是C6-C18,优选C8-C10,直链或支链、饱和或不饱和烃基;
(g)具有下列化学通式的烷基聚苷的阴离子酯衍生物
其中聚苷是由葡萄糖或其它单-、二-或多糖生成的,n是聚合度且通常在1至3的范围内,R18是C6-C18,优选C8-C10,直链或支链、饱和或不饱和烃基,X表示由二或三羧酸,优选柠檬酸、酒石酸或磺基琥珀酸衍生成的羧酸盐部分(参看欧洲专利EP 0 258 814B1);或
(h)它们的混合物。
草甘膦的MMA和DMA盐提供了优于已经商业化的其它盐的某些优点。它们与较不容易形成对眼刺激的高度乙氧基化的烷基胺乙氧基化物相容。此外,草甘膦K盐与其它除草剂酸盐(例如,triclopyr,2,4-D)的储罐混合物可能形成可溶性很差的第二种除草剂酸的钾盐,由此降低了第二种除草剂的生物有效性。MMA和DMA盐克服了这种不相容性问题。此外,MMA和DMA盐的分子量比IPA或MEA盐低。由此,在给定的盐浓度下,草甘膦的MMA或DMA盐具有比IPA盐或近来描述的MEA盐高的草甘膦酸当量。
在另一形式中,本发明提供了一种用除草制剂处理植物的方法。所述制剂可以如上所述提供。所述制剂通常作为苗后(post-emergent)除草剂施用。所述制剂可以作为高浓溶液施用或优选在施用到植物之前用水稀释。此外,草甘膦的MMA盐特别在控制白藜(lambsquarters)方面比其它盐有效。
一般而言,本发明涉及含有草甘膦的MMA或DMA盐和有效的表面活性剂的高强度除草浓缩组合物。更具体地,本发明提供了一种高强度除草浓缩组合物,所述组合物含有:(a)水,(b)草甘膦,主要是MMA或DMA盐形式,以每升组合物高于350克酸当量(gae/l)的量溶于水,和(c)总量为每升组合物20至200克(g/l)的至少一种表面活性剂。
除草制剂包括足够量的能提供高强度制剂的草甘膦盐。在优选具体实施方式中,以草甘膦酸当量计,所述的高强度除草制剂包含高于350gae/l的草甘膦盐;更优选地,以草甘膦酸当量计,高强度除草制剂包含高于440gae/l的草甘膦盐;最优选地,以草甘膦酸当量计,高强度除草制剂包含高于480gae/l的草甘膦盐。
在优选具体实施方式中,本发明包括在高温下具有储存稳定性的高强度除草制剂。也就是说,所述制剂在储存条件下形成不呈现混浊的澄清均质稳定溶液。更优选地,本发明的制剂在高于或等于50℃,更优选在高于或等于60℃的温度下稳定。
此外,除草制剂在低温下不会表现出任何组分的分离或沉淀(或结晶)。例如,高强度制剂在低于10℃,更优选低于0℃的温度下仍然是澄清溶液。
上文中的术语“主要”是指以酸当量表示的草甘膦重量的至少50%,优选至少75%,更优选至少90%是MMA或DMA盐。剩余部分可以由其它盐构成,例如IPA盐,只要该制剂仍然是在至少高达50℃的温度下稳定并在低至10℃的温度下不会有任何沉淀的澄清均质溶液。
高强度除草制剂还包括增效量的表面活性剂。在优选具体实施方式中,选择表面活性剂以使其在溶液中与除草制剂中的高浓度草甘膦相容。在本申请中,使用术语“相容”时,本领域技术人员能够理解在其含义中包括下述意思——即所得溶液不会在制剂中表现出相分离或沉淀,所述制剂最初观察为混浊形式,并通常在特定温度下测定。
本发明中使用的表面活性剂优选包括一种或多种下列类型的化合物:含有8至22个碳原子和总共1-20个烯化氧基团的烷氧基化烷基胺表面活性剂,例如分别作为EthomeenTMC/15、Ethomeen T/15和Ethomeen T/20从Akzo Nobel购得的那些;醚胺表面活性剂,例如TomahE-14-2、Tomah E-14-5和Tomah E-17-5;季铵表面活性剂,例如EthoquadTM C/12、Ethoquad 18/12或Tomah Q-14-2;两性表面活性剂,例如来自Rhodia的Geronol CF/AS 30,或来自Goldschmidt的TegoTMBetaine F50;脂肪醇乙氧基化物,例如TergitolTM 15S20;脂肪醇乙氧基化物磷酸酯,例如来自Rhodia的Geranol CF/AR;烷基聚苷,例如Akzo Nobel AG 6202或AG 6210;或烷基聚苷的阴离子酯衍生物,例如EucarolTM AGE表面活性剂。
表面活性剂可以以所需浓度包含在除草制剂中。优选地,所需浓度足以提高所得制剂的除草活性,使其高于对不含表面活性剂的相同除草制剂所观察到的除草活性。更优选地,除草制剂包含20g/l至200g/l,更优选100g/l至150g/l的表面活性剂。
意外地测定,通过审慎地选择与草甘膦的MMA或DMA盐结合的特定表面活性剂,就可以极大地改进所得除草制剂的粘度。最优选的是表面活性剂的混合物。例如,牛油脂肪胺乙氧基化物与GeronolCF/AS 30之类的两性表面活性剂的共混物表现出对粘度的协同作用,也就是说,含表面活性剂共混物的制剂的粘度明显低于含相同浓度的单个表面活性剂的制剂。在优选具体实施方式中,除草制剂表现出低于140厘泊(140milliPascal·s;mpa·s),更优选低于100厘泊(100mpa·s)的粘度。
此外,表面活性剂与草甘膦的MMA或DMA盐的选定组合在高浓度制剂中仍然相容。所得水溶液组合物可以用作高强度除草制剂。
本文所述的制剂可以以足以引发除草效应的量施用到植物上。例如,按照本发明制备的制剂可以作为水溶液施用到植物上,包括植物的叶、干、枝、花和/或果实。除草制剂可以以足以抑制植物生长或杀灭单株植物的除草有效量施用。
按照本发明制备的农业组合物作为除草组合物对多种杂草都极为有效。本发明的制剂可以原样使用,也可以与其它组分结合使用,这些组分包括常用来配制成的农产品的农用助剂,例如防沫剂、相容性试剂、螯合剂、中和剂和缓冲剂、防腐剂、染料、增香剂、渗透助剂、湿润剂、铺展剂、分散剂、增稠剂、凝固点降低剂、抗菌剂、作物油、其它生物上和/或农业上活性组分等。浓缩的农业制剂通常用水稀释,然后通过本领域技术人员公知的常规方式施用。
实施例
实施例1:高强度草甘膦DMA盐制剂的制备
使408克草甘膦人造湿滤饼与283克40%的二甲胺水溶液在61克水中反应,由此制备草甘膦DMA盐浓缩物。该浓缩物含有62%的草甘膦DMA盐。该溶液的密度为1.259g/ml。
通过将所得浓缩物与适当量的表面活性剂和水共混来制备制剂。表1给出的实施例证实了本发明。
表1
制剂实施例
制剂号 | g/l草甘膦算当量,作为DMA盐 | 表面活性剂 |
1 | 360 | Ethomeen C/15,100g/l |
2 | 360 | Ethoquad C/12,100g/l |
3 | 360 | Tomah Q-14-2,100g/l |
4 | 360 | PEG-20牛油脂肪胺,100g/l |
5 | 540 | PEG-10牛油脂肪胺,100g/l |
6 | 480 | PEG-5牛油脂肪胺,110g/l |
7 | 480 | PEG-10牛油脂肪胺,150g/l |
8 | 480 | Geronol CF/AS 30,150g/l |
9 | 480 | Geronol CF/AS 30,120g/l+PEG-10牛油脂肪胺,30g/l |
10 | 480 | Akzo Nobel AG 6202,130g/l |
11 | 480 | Geronol CF/AR,120g/l |
12 | 480 | Eucarol AGE/ET,100g/l |
13 | 480 | Tego Betaine F50,80g/l+PEG-10牛油脂肪胺,60g/l |
*Ethomeen C/15为PEG-5椰油烷基胺
*Ethoquad C/12为椰油烷基甲基双(2-羟基乙基)氯化铵
*Tomah Q-14-2为异癸氧基丙基甲基双(2-羟基乙基)氯化铵
*Geronol CF/AS 30为C12-C14烷基二甲基甜菜碱
*Akzo Nobel AG 6202为烷基多聚葡萄糖
*Geronol CF/AR为磷酸醇乙氧基化物酯
*Eucarol AGE/ET为酒石酸烷基多聚葡萄糖酯
*Tego Betaine F50为柯卡酰氨基丙基甜菜碱
所有制剂都形成澄清均质液体。这些制剂可以在54℃下稳定储存2周,没有相分离,并可以在-10℃下稳定储存2周,没有结晶。上述制剂的浊点高于60℃。
用布鲁克菲尔德LVT粘度计或Bohlin CS-50流变仪测量样品制剂的粘度并与市售高强度制剂进行比较。令人惊奇地,高强度草甘膦DMA盐制剂的粘度明显低于市售标准品(参看表2)。意外地,通过将4份制剂8与1份制剂7共混制得的制剂9的粘度比单独的制剂8和制剂7都低。按照简单混合规则,预期粘度为249mPa.s,而在相同的表面活性剂总浓度下,实际粘度仅为59mPa.s。这证实了将两种表面活性剂共混的协同粘度作用。
表2
制剂粘度
样品 | 粘度 |
Roundup UltraMAX(USA)(445gae/l草甘膦IPA) | 185mPa.s |
Roundup MAX(Australia)(510gae/l草甘膦MEA) | 176mPa.s |
Glyphomax Plus(USA)(356gae/l草甘膦IPA) | 56mPa.s |
5(540gae/l草甘膦DMA-盐) | 100mPa.s |
6(480gae/l草甘膦DMA-盐) | 96mPa.s |
7(480gae/l草甘膦DMA-盐) | 82mPa.s |
8(480gae/l草甘膦DMA-盐) | 291mPa.s |
9(480gae/l草甘膦DMA-盐) | 59mPa.s |
10(480gae/l草甘膦DMA-盐) | 72mPa.s |
11(480gae/l草甘膦DMA-盐) | 42mPa.s |
12(480gae/l草甘膦DMA-盐) | 32mPa.s |
13(480gae/l草甘膦DMA-盐) | 68mPa.s |
实施例2:
高强度草甘膦DMA盐制剂的效力
在温室试验中评测草甘膦DMA盐制剂对5双子叶植物和3单子叶杂草的效力。以100、200、400、600和800gae/ha施用制剂,用RoundupUltraTM Herbicide、Roundup UltraMAXTM和RoundupWeatherMAXTMHerbicide(都是Monsanto)作为标准处理品。喷洒体积为187升/公顷(l/ha);施用时,杂草处于3叶期。每一处理都重复3次;在施用后14天时通过对控制百分比的目测进行评测。
表3显示在600gae/ha的施药量下对每种杂草类的控制百分比。
表3
在600gae/ha.的施药量下与Roundup Ultra(356gae/l草甘膦IPA盐)相比,实施例制剂(360gae/l草甘膦DMA盐)的生物效力,在施用后14天时测量的控制百分比
制剂 | IPOHE | CHEAL | EPHHL | ABUTH | CASOB | ECHCG | AVEFA | AGGRE | 平均 |
RoundupUltra | 41.7% | 80.9% | 84.2% | 80.0% | 70.0% | 85.9% | 53.3% | 51.7% | 68.4% |
1 | 43.3% | 89.2% | 90.0% | 76.7% | 80.8% | 93.3% | 74.2% | 78.4% | 78.2% |
2 | 50.0% | 85.9% | 89.0% | 79.2% | 78.4% | 90.7% | 68.3% | 69.2% | 76.3% |
3 | 43.3% | 84.2% | 92.5% | 80.0% | 78.4% | 88.2% | 68.4% | 65.9% | 75.1% |
IPOHE Ipomoea hederacea(牵牛花) Morningglory(牵牛花)
CHEAL Chenopodium album(藜科) Lambsquarter(白藜)
EPHHL Euphorbia heterophylla(猩猩 wild pointsettia(猩猩草)
草)
ABUTH Abutilontheophrasti(苘麻) velvet leaf(苘麻)
CASOB Cassia obtusifolia(决明) Sicklepod(决明)
ECHCG Echinochloa crus-galli(稗草) Barnyardgrass(稗草)
AVEFA Avena fatua(野燕麦) wild oat(野燕麦)
AGGRE Agropyron repens(匍匐冰草) Quackgrass(匍匐冰草)
平均而言,在受试的8个物种中,DMA盐制剂(仅含100g/l表面活性剂)的效力优于市售IPA盐制剂(包含180g/l表面活性剂)的效力。
表4显示,与市售高强度制剂Roundup UltraMAX相比,480gae/l草甘膦DMA盐制剂6的生物效力。在所有种类中,DMA盐制剂的表现都优于市售IPA盐制剂。
表4
在600gae/ha.的施药率下与商业标准Roundup UltraMAX(445gae/l草甘膦IPA盐)相比,实施例制剂6(480gae/l草甘膦DMA盐)的生物效力。施用后14天时测量的控制百分比
制剂 | IPOHE | CHEAL | EPHHL | ABUTH | CASOB | ECHCG | AVEFA | AGGRE | 平均 |
RoundupUltraMAX | 61.7% | 83.3% | 94.7% | 85.0% | 66.7% | 99.0% | 66.7% | 53.3% | 76.3% |
6 | 78.3% | 85.0% | 99.0% | 86.7% | 68.3% | 91.0% | 81.7% | 83.5% |
平均而言,在8个受试物种中,DMA盐制剂的效力优于市售IPA盐制剂的效力。
表5对比了480gae/l草甘膦DMA盐制剂7和540gae/l草甘膦DMA盐制剂5与市售高强度制剂Roundup WeatherMAX(540gae/l草甘膦K盐)的生物效力。在所有物种中,DMA盐制剂的表现都优于市售K盐制剂。
表5
在600gae/ha.的施药率下与商业标准Roundup WeatherMAX(540gae/l草甘膦K盐)相比,实施例制剂5(540gae/l草甘膦DMA盐)和7(480gae/l草甘膦DMA盐)的生物效力。施用后14天时测量的控制百分比
制剂 | IPOHE | CHEAL | EPHHL | ABUTH | CASOB | ECHCG | AVEFA | AGGRE | 平均 |
RoundupWeatherMAX | 43.3% | 81.7% | 91.7% | 75.0% | 86.7% | 75.0% | 88.3% | 97.0% | 79.8 |
5 | 61.7% | 83.3% | 98.3% | 91.7% | 83.3% | 86.7% | 92.0% | 90.0% | 85.9 |
7 | 55.0% | 76.7% | 97.0% | 97.3% | 83.3% | 95.0% | 90.0% | 99.3% | 86.7 |
平均而言,在8个受试物种中,DMA盐制剂的效力优于市售IPA盐制剂的效力。
在另一温室试验中,将分别与DMA4(456g/l 2,4-D酸当量的DMA盐形式)和Garlon 3A(360g/ltriclopyr酸当量的三乙胺[TEA]盐形式)混合的草甘膦DMA盐溶液的效力与在相同混合物中的草甘膦K盐溶液的效力进行比较。
用所需量的水稀释草甘膦DMA盐提浓物和草甘膦K盐提浓物以制备各自含有480g/l草甘膦酸当量的溶液,由此制备草甘膦盐溶液。
用每种制剂以及表6列出的混合物喷洒五个阔叶物种(IPOHE、CHEAL、EPHHL、ABUTH和CASOB)。
使用Colby’s方程分析除草剂相互作用。这种用于预期的混合物响应的方程是:
y1+2=y1+y2-(y1y2)/100
其中y1+2是预期的混合物响应,y1和y2是单种除草剂的控制百分比值。
表6
在420gae/ha草甘膦和140gae/ha第二除草剂的施药率下,与第二除草剂混合的草甘膦DMA盐(480gae/l草甘膦DMA盐)和草甘膦K盐(480gae/l草甘膦K盐)的生物效力。施用3天后测量控制百分比并对5种物种取平均值
%实际控制 | %预期控制 | 实际-预期控制 | |
420gae/ha草甘膦K盐 | 35.7 | ||
420gae/ha草甘膦DMA盐 | 35.7 | ||
140gae/ha 2,4-D DMA盐 | 47.0 | ||
140gae/ha triclopyr TEA盐 | 55.0 | ||
420gae/ha草甘膦K盐+140gae/ha 2,4-D DMA盐 | 50.7 | 65.9 | -15.2 |
420gae/ha草甘膦DMA盐+140gae/ha 2,4-D DMA盐 | 67.0 | 65.9 | 1.1 |
420gae/ha草甘膦K盐+140gae/ha triclopyr TEA盐 | 57.7 | 71.1 | -13.4 |
420gae/ha草甘膦DMA盐+140gae/ha triclopyr TEA盐 | 72.0 | 71.1 | 0.9 |
结果表明,如与使用Colby’s方程得出的预期控制相比,实际控制的降低说明草甘膦K盐对2,4-D DMA和triclopyr TEA都有对抗作用。相反,草甘膦DMA盐因其实际控制与预期控制相当,所以没有显示出对抗性,由此相比草甘膦K盐获得了明显的改进。
实施例3:
高强度草甘膦MMA盐制剂的制备
使505克草甘膦人造湿滤饼与238克41%的甲胺水溶液在121克水中反应,由此制备草甘膦MMA盐浓缩物。该浓缩物含有62%的草甘膦MMA盐。该溶液的密度为1.302g/ml。
通过将该浓缩物与适当量的表面活性剂和水共混来制备制剂。表7给出的实施例证实了本发明。
表7
制剂实施例
制剂号 | g/l草甘膦酸当量作为MMA盐 | 表面活性剂 |
14 | 480 | PEG-5牛油脂肪胺,150g/l |
15 | 480 | PEG-10牛油脂肪胺,150g/l |
16 | 480 | Geronol CF/AS 30,150g/l |
17 | 480 | Akzo Nobel AG 6210,130g/l |
18 | 480 | Geronol CF/AR,120g/l |
19 | 480 | Eucarol AGE/EC,100g/l |
20 | 480 | PEG-10,牛油脂肪胺,50g/lGeronol CF/AS 30,100g/l |
21 | 480 | PEG-10牛油脂肪胺,50g/lPEG-5牛油脂肪胺,20g/lGeronol CF/AS 30,100g/l |
22 | 540 | PEG-10牛油脂肪胺,33g/lPEG-5牛油脂肪胺,17g/lGeronol CF/AS 30,100g/l |
*Geronol CF/AS 30为C12-C14烷基二甲基甜菜碱
*Akzo Nobel AG 6202为烷基多聚葡萄糖
*Geronol CF/AR为脂肪醇乙氧基化物磷酸酯
*Eucarol AGE/EC为烷基多聚葡萄糖柠檬酸酯
所有制剂都形成澄清均质液体。这些制剂可以在54℃下稳定储存2周,没有相分离,并可以在-10℃下稳定储存2周,没有结晶。上述制剂的浊点高于60℃。
用布鲁克菲尔德LVT粘度计或Bohlin CS-50流变仪测量样品制剂的粘度并与市售高强度制剂进行比较。令人惊奇地,高强度草甘膦MMA盐制剂的粘度明显低于市售标准品(参看表8)。
表8
制剂粘度粘度测量,Brookfield LVT,Spindle#2在20℃下
样品 | 粘度(mPa.s) |
Roundup UltraMAX(USA)(445gae/l草甘膦IPA) | 161 |
Roundup MAX(Australia)(510gae/l草甘膦MEA) | 153 |
Roundup WeatherMAX(USA)(540gae/l草甘膦钾) | 52 |
15(480gae/l草甘膦MMA-盐) | 56 |
16(480gae/l草甘膦MMA-盐) | 163 |
17(480gae/l草甘膦MMA-盐) | 41 |
18(480gae/l草甘膦MMA-盐) | 25 |
19(480gae/l草甘膦MMA-盐) | 28 |
20(480gae/l草甘膦MMA-盐) | 28 |
21(480gae/l草甘膦MMA-盐) | 45 |
22(540gae/l草甘膦MMA-盐) | 90 |
意外地,通过将1份制剂15与2份制剂16共混制得的样品20的粘度比单独的制剂15和制剂16都低。如果粘度符合简单混合规则,那么预期粘度应为130mPa.s。而实测粘度仅为28mPa.s,证实了将两种表面活性剂共混的协同作用。
实施例4:
高强度草甘膦MMA盐制剂的效力
在温室试验中,评测草甘膦MMA盐制剂对5双子叶植物和3单子叶植物杂草的效力。以100、200、400、600和800gae/ha施用制剂,用Roundup WeatherMAXTMHerbicide(Monsanto)作为标准处理品。喷洒体积为140升/公顷(l/ha);施用时,杂草处于3叶期。每一处理都重复3次;在施用后14天时通过对控制百分比的目测进行评测。
表9显示在400gae/ha的施药率下对每种杂草类的控制百分比。
表9
在400gae/ha.的施药率下与Roundup WeatherMAX(540gae/l草甘膦K盐)相比,实施例制剂(480/540gae/l草甘膦MMA盐)的生物效力。施用14天后测量的控制百分比
制剂 | IPOHE | CHEAL | EPHHL | ABUTH | CASOB | ECHCG | AVEFA | AGGRE | 平均 |
RoundupWeatherMAX | 73.3 | 70.0 | 70.0 | 70.0 | 70.0 | 76.0 | 56.7 | 63.3 | 68.7% |
20 | 66.7 | 98.3 | 90.0 | 60.0 | 75.0 | 84.7 | 75.0 | 71.7 | 77.7% |
21 | 63.3 | 99.0 | 89.7 | 68.3 | 75.0 | 90.0 | 63.3 | 75.0 | 78.0% |
22 | 68.3 | 98.3 | 92.3 | 75.0 | 60.0 | 97.0 | 76.7 | 73.3 | 80.1% |
20:480gae/l草甘膦MMA盐
21:480gae/l草甘膦MMA盐
22:540gae/l草甘膦MMA盐
IPOHE Ipomoea hederacea(牵牛花) Morningglory(牵牛花)
CHEAL Chenopodium album(藜科) Lambsquarter(白藜)
EPHHL Euphorbia heterophylla(猩猩 wild pointsettia(猩猩草)
草)
ABUTH Abutilon theophrasti(苘麻) velvet leaf(苘麻)
CASOB Cassia obtusifolia(决明) sicklepod(决明)
ECHCG Echinochloa crus-galli(稗草) Barnyardgrass(稗草)
AVEFA Avena farua(野燕麦) wild oat(野燕麦)
AGGRE Agropyron repens(匍匐冰草) Quackgrass(匍匐冰草)
平均而言,在受试的8个物种中,MMA盐制剂的效力优于市售草甘膦K盐制剂的效力。
表10显示,在白藜(Midwest USA地区特别麻烦的一种杂草)上,与市售高强度制剂Roundup WeatherMAX相比,在施用草甘膦MMA盐制剂20、21和22后9天时的GR90值。
表10
与Roundup WeatherMAX(540gae/l草甘膦K盐)相比,实施例制剂(480/540gae/l草甘膦MMA盐)在白藜上的GR90值
高 | 低 | GR90 | |
Roundup WeatherMAX | 724gae/ha | 476gae/ha | 587gae/ha |
MMA 480gae/l(20) | 513gae/ha | 351gae/ha | 425gae/ha |
MMA 480gae/l(21) | 391gae/ha | 222gae/ha | 295gae/ha |
MMA 540gae/l(22) | 472gae/ha | 303gae/ha | 378gae/ha |
GR90值是提供控制90%的白藜所需的以gae/ha为单位的量,草甘膦MMA制剂的GR90值与市售Roundup WeatherMAX制剂相比明显较低(表10中的高和低值反映95%置信区间)。特别地,为了获得相同水平的白藜控制,草甘膦MMA盐制剂20要求的每公顷草甘膦酸当量仅为市售标准Roundup WeatherMAX的一半。
Claims (7)
1.一种高强度除草浓缩组合物,所述组合物含有:(a)水,(b)草甘膦,主要是MMA或DMA盐形式,以每升组合物高于350克酸当量的量溶于水,和(c)总量为每升组合物20至200克的至少一种表面活性剂。
2.根据权利要求1所述的组合物,其中,所述组合物含有每升组合物高于440克酸当量的草甘膦。
3.根据权利要求1所述的组合物,所述组合物具有低于140厘泊的粘度。
4.根据权利要求1的组合物,其中所述表面活性剂是
(a)具有下列化学通式的烷基胺和烷基醚胺表面活性剂
其中R1是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,R2和R3独立地为C1-C4烷基,优选甲基,或总共含有2至22个烯化氧单元,优选环氧乙烷单元的聚氧化烯链;
(b)具有下列化学通式的季铵表面活性剂
其中Z-是农业上可接受的阴离子,例如氯根、溴根、碘根、硫酸根或乙酸根,R4、R5、R6和R7包括,但不限于如下所述:
(i)R4是苄基或C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,且R5、R6和R7独立地为C1-C4烷基,优选甲基;
(ii)R4和R5独立地为C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,且R6和R7独立地为C1-C4烷基,优选甲基;
(iii)R4是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,R5是含有2至22个,优选2至15个C2-C4烯化氧单元,优选环氧乙烷单元的聚氧化烯链,且R6和R7独立地为C1-C4烷基,优选甲基;或
(iv)R4是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,其中任选插入一条或多条醚键,R5和R6是含有2至22个,优选2至15个C2-C4烯化氧单元,优选环氧乙烷单元的聚氧化烯链,且R7是C1-C4烷基,优选甲基;
(c)具有下列化学通式的两性表面活性剂
R8R9R10N+-(CH2)nCOO-
其中R8、R9、R10和n包括,但不限于如下所述:
(v)R8是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,且R9和R10独立地为C1-C4烷基,优选甲基,或氢原子;n是1至5的整数;或
(vi)R8是[R11-CONH-(CH2)x-]基团,其中R11是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,x是1至5的整数,且R9和R10独立地为C1-C4烷基,优选甲基,或氢原子;n是1至5的整数;
(d)具有下列化学通式的脂肪醇乙氧基化物
R12-O-(CH2-CHR13-O)n-R14
其中通式R12是C8-C24,优选C12-C18,直链或支链、饱和或不饱和烃基,R13独立地代表氢原子或甲基或乙基基团,优选氢原子,n是2至50,优选10至30的整数,且R14是C1-C4烷基,优选甲基,或氢原子;
(e)具有下列化学通式的脂肪醇乙氧基化物磷酸酯
[R15-O-(CH2-CHR16-O)n]3-m-P(=O)(OM)m
其中通式R15是C6-C20,优选C8-C18,直链或支链、饱和或不饱和烃基,R16独立地代表氢原子或甲基或乙基基团,优选氢原子,n是0至10,优选2至10的整数,M独立地代表氢原子、碱金属或碱土金属、铵或烷基铵离子,且m是1至2的整数;
(f)具有下列化学通式的烷基聚苷
其中聚苷是由葡萄糖或其它单-、二-或多糖衍生成的,n是聚合度且典型地在1至3的范围内,R17是C6-C18,优选C8-C10,直链或支链、饱和或不饱和烃基;
(g)具有下列化学通式的烷基聚苷的阴离子酯衍生物
其中聚苷是由葡萄糖或其它单-、二-或多糖生成的,n是聚合度且典型地在1至3的范围内,R18是C6-C18,优选C8-C10,直链或支链、饱和或不饱和烃基,X代表由二或三羧酸,优选柠檬酸、酒石酸或磺基琥珀酸衍生成的羧酸盐部分;或
(h)它们的混合物。
5.根据权利要求4所述的组合物,其中表面活性剂是牛油脂肪胺乙氧基化物共混物与具有下面通式的两性表面活性剂共混物的混合物,
R8R9R10N+-(CH2)nCOO-
其中R8是C12-C14烃基,R9和R10都是CH3,n是1。
6.根据权利要求5所述的组合物,其中所述组合物的粘度低于100厘泊,而且其含有每升组合物高于480克酸当量的草甘膦。
7.一种控制不需要的植被的方法,所述方法包括对植被施用用水稀释的权利要求1所述的组合物。
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-
2004
- 2004-02-06 BR BRPI0413266A patent/BRPI0413266B8/pt active IP Right Grant
- 2004-02-06 EP EP04709001.4A patent/EP1651048B1/en not_active Expired - Lifetime
- 2004-02-06 CN CN2004800209628A patent/CN1826055B/zh not_active Expired - Lifetime
- 2004-02-06 ES ES04709001.4T patent/ES2593006T3/es not_active Expired - Lifetime
- 2004-02-06 AU AU2004264781A patent/AU2004264781B2/en not_active Expired
- 2004-02-06 HU HUE04709001A patent/HUE030940T2/en unknown
- 2004-02-06 ZA ZA200600081A patent/ZA200600081B/en unknown
- 2004-02-06 WO PCT/US2004/003472 patent/WO2005016002A1/en active Application Filing
- 2004-02-06 PL PL378935A patent/PL221513B1/pl unknown
- 2004-02-06 PT PT47090014T patent/PT1651048T/pt unknown
- 2004-02-06 US US10/774,238 patent/US7316990B2/en active Active
- 2004-02-06 MX MXPA06001389A patent/MXPA06001389A/es active IP Right Grant
- 2004-02-06 RU RU2006106709/15A patent/RU2336700C2/ru active
- 2004-02-06 UA UAA200602389A patent/UA80911C2/xx unknown
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- 2004-02-06 JP JP2006522536A patent/JP4686457B2/ja not_active Expired - Lifetime
- 2004-02-24 AR ARP040100577A patent/AR043383A1/es active IP Right Grant
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Also Published As
Publication number | Publication date |
---|---|
ZA200600081B (en) | 2007-03-28 |
CN1826055B (zh) | 2010-05-26 |
ES2593006T3 (es) | 2016-12-05 |
JP2007501226A (ja) | 2007-01-25 |
EP1651048B1 (en) | 2016-08-17 |
CY1118428T1 (el) | 2017-06-28 |
BRPI0413266B1 (pt) | 2015-07-21 |
PL378935A1 (pl) | 2006-06-12 |
US7316990B2 (en) | 2008-01-08 |
CO5650202A2 (es) | 2006-06-30 |
AR043383A1 (es) | 2005-07-27 |
CA2531340C (en) | 2011-08-09 |
EP1651048A1 (en) | 2006-05-03 |
RU2336700C2 (ru) | 2008-10-27 |
MXPA06001389A (es) | 2006-05-15 |
JP4686457B2 (ja) | 2011-05-25 |
UA80911C2 (en) | 2007-11-12 |
HUE030940T2 (en) | 2017-06-28 |
BRPI0413266A (pt) | 2006-10-10 |
BRPI0413266B8 (pt) | 2022-06-28 |
AU2004264781A1 (en) | 2005-02-24 |
PL221513B1 (pl) | 2016-04-29 |
WO2005016002A1 (en) | 2005-02-24 |
AU2004264781B2 (en) | 2010-02-18 |
RU2006106709A (ru) | 2006-07-27 |
US20050032649A1 (en) | 2005-02-10 |
PT1651048T (pt) | 2016-09-26 |
CA2531340A1 (en) | 2005-02-24 |
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