CN115245163A - 环境友好含氟非离子表面活性剂在农药中的应用 - Google Patents

环境友好含氟非离子表面活性剂在农药中的应用 Download PDF

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CN115245163A
CN115245163A CN202110463672.6A CN202110463672A CN115245163A CN 115245163 A CN115245163 A CN 115245163A CN 202110463672 A CN202110463672 A CN 202110463672A CN 115245163 A CN115245163 A CN 115245163A
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nonionic surfactant
containing nonionic
fluorine
environment
surface tension
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汪清民
张静静
王瑞国
宋红健
刘玉秀
寇俊杰
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Nankai University
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Abstract

本发明涉及含氟非离子表面活性剂应用领域，具体涉及一种环境友好含氟非离子表面活性剂作为增效剂在农药除草剂和杀虫剂中的应用，结构式中各基团的意义见说明书。本发明的含氟非离子表面活性剂作为增效剂，在农药除草剂和杀虫剂中能起到明显的增效作用，增效效果可以达到甚至超过商品化Si‑408，而且本发明中含氟非离子表面活性剂在药液中的稳定性优于商品化Si‑408。

Description

环境友好含氟非离子表面活性剂在农药中的应用
技术领域
本发明涉及含氟非离子表面活性剂技术领域，具体涉及一种环境友好含氟非离子表面活性剂作为增效剂在农药除草剂和杀虫剂中的应用。
背景技术
含氟表面活性剂作为特种表面活性剂中重要的一类，是指碳氢表面活性剂碳氢链上的氢原子全部或部分被氟原子取代，形成以氟碳链为疏水基的一类表面活性剂。氟碳键的特殊结构赋予了含氟表面活性剂具有常规表面活性剂不可比拟的性质：高表面活性、高化学稳定性、高耐热稳定性以及氟碳链既憎水又憎油的特性。但是，长氟碳链(连有氟的碳原子的个数大于等于8)的含氟化合物难以在环境中降解，并且具有生物积累性，会沿食物链在生物体内富集，危害人类健康。比如全氟辛烷磺酸(PFOS)在人体内的“半排出时间”长达8.7年，不但会造成呼吸系统的伤害，甚至会导致新生婴儿死亡。所以，研究含碳氟短链的表面活性剂具有重要的意义。
含氟表面活性剂是迄今为止所有表面活性剂中表面活性最高的一类，其水溶液的临界胶束浓度(CMC)和临界胶束浓度时的表面张力(γcmc)都远低于碳氢表面活性剂，广泛应用于各种领域，包括生物医学、消防、化妆品、农用化学品等。在农药领域，喷雾是病虫害防治的重要手段，在喷雾药液中加入表面活性剂作为增效剂可以降低其表面张力，提高药液在靶标植株表面的润湿性，更好地促进药液的铺展，从而提高农药的利用率。目前，有机硅助剂作为增效剂在农药喷雾中应用较多，其在多种靶标植株表面都具有极强的润湿扩展性，Si-408在水溶液中含量为0.1wt.％时，可使水的表面张力降低至20mN/m左右。而含氟表面活性剂作为增效剂在农药中的应用还没有报道，主要原因是含氟表面活性剂成本较高。
因此，研制性能优异、环境友好和廉价易得的含氟非离子表面活性剂在农药中的应用具有十分重要的意义。
发明内容
本发明的目的是提供了一种新的、环境友好、含氟非离子表面活性剂作为增效剂在农药中的应用。
为达到发明的目的，本发明在进行分子设计时，选择了具有优异的生物相容性、生物降解性的聚乙二醇和环境友好的连有氟的碳原子的个数小于等于6的氟醇来制备具有环境友好和表面活性可调控的含氟非离子表面活性剂，其结构如下：
Figure BSA0000240702450000011
式中R为CH3、
Figure BSA0000240702450000021
Rf为1～6个碳的氟烷基链，m整数，1≤m≤115。
本发明提供一种农药组合物，所述农药组合物包含环境友好含氟非离子表面活性剂和除草剂制剂，其中环境友好含氟非离子表面活性剂与除草剂制剂的质量比为(0.005～0.1)∶100。
上述农药组合物中，所述除草剂活性成分为草铵膦、草甘膦异丙胺盐、草除灵、丁草胺、敌草隆中的一种。
本发明提供一种农药组合物，所述农药组合物包含环境友好含氟非离子表面活性剂和杀虫剂制剂，其中环境友好含氟非离子表面活性剂与除草剂制剂的质量比为(0.005～0.1)∶100。
上述农药组合物中，所述杀虫剂活性成分为茚虫威、氯虫苯甲酰胺、甲氨基阿维菌素苯甲酸盐、螺虫乙酯、氟虫腈中的一种。
本发明选择商品化的Si-408作为对照进行比较，通过测量上述农药组合物喷洒药液的静态表面张力、动态表面张力和接触角，并进行室内活性测试，研究环境友好含氟非离子表面活性剂的增效效果。
本发明提供了一种环境友好含氟非离子表面活性剂作为农药增效剂的使用方法，其特征在于在市售除草剂和杀虫剂稀释阶段添加环境友好含氟非离子表面活性剂进行混合使用。
本发明具有以下优点：
1.本发明提供的一种环境友好含氟非离子表面活性剂降低表面张力的效率优异，临界胶束浓度为0.0001g/L～0.8g/L。表面张力为15mN/m～35mN/m，低于商品化的非离子表面活性剂的表面张力。
2.本发明提供的一种环境友好含氟非离子表面活性剂对生态安全，对斑马鱼急性毒性测定结果均为低毒。
3.本发明提供的一种环境友好含氟非离子表面活性剂作为增效剂能有效降低药液的表面张力，使雾滴能有效润湿铺展于作物叶片，促进药液渗透到作用部位，提高防治效果。
4.本发明通过测定药液的静态表面张力、动态表面张力和接触角，并经过室内生物活性测试，得出一种环境友好含氟非离子表面活性剂作为草铵膦、草甘膦异丙胺盐、草除灵、丁草胺、敌草隆制剂的添加剂，对这些除草剂具有增效作用。
5.本发明通过测定药液的静态表面张力、动态表面张力和接触角，并经过室内生物活性测试，得出一种环境友好含氟非离子表面活性剂作为茚虫威、氯虫苯甲酰胺、甲氨基阿维菌素苯甲酸盐、螺虫乙酯、氟虫腈制剂的添加剂，对杀虫剂具有增效作用。
6.本发明提供的一种环境友好含氟非离子表面活性剂在实际应用中作为增效剂不仅能起到明显的增效作用，而且增效效果可以达到甚至超过商品化Si-408。
7.本发明提供的一种环境友好含氟非离子表面活性剂在实际应用中作为增效剂的稳定性优于Si-408。
具体实施方式
下面给出实施例以对本发明作进一步说明。有必要指出的是以下实施例不能理解为对本发明保护范围的限制，如果该领域的技术熟练人员根据上述本发明内容对本发明做出一些非本质的改进和调整，仍属于本发明保护的范围。
另外，需要说明的是：
1.所述环境友好含氟非离子表面活性剂表面张力的测定方法：配置一系列不同浓度的环境友好含氟表面活性剂，采用吊环法由JK99M全自动静态表面张力仪进行表面张力测试(外径20.30mm，铂丝0.30mm，周长61.89mm，密度0.998g/cm3，温度25±1℃)。采用KrussBP100表面张力仪(最大气泡压力法)测定了动态表面张力。仪器在测试前后均用纯水校准。
2.所述环境友好含氟非离子表面活性剂接触角的测定方法：接触角为表面活性剂溶液与固体表面的接触角度，采用OCA 25接触角测量仪(座滴法)测定了农药喷洒液在玉米叶上的接触角，研究了含表面活性剂农药喷洒液在玉米叶上的润湿性，测试温度为25±1℃，每一个样品的接触角都测定了5遍，然后选取测量角度为中间值那一次作为最终结果。
实施例1
供试除草剂30％草甘膦异丙胺盐水剂的用量为350g a.i/hm2，选用环境友好的聚乙二醇分子量为200g/mol，氟醇为十二氟庚醇的含氟非离子表面活性剂作为增效剂，其中30％草甘膦异丙胺盐水剂喷洒液与环境友好含氟非离子表面活性剂的质量比为100∶0.03。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例2
供试除草剂30％草甘膦异丙胺盐水剂的用量为350g a.i/hm2，选用环境友好的聚乙二醇分子量为500g/mol，氟醇为全氟己-1-醇的含氟非离子表面活性剂作为增效剂，其中30％草甘膦异丙胺盐水剂喷洒液与含氟非离子表面活性剂的质量比为100∶0.05。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例3
空白对照，不添加环境友好含氟非离子表面活性剂。供试除草剂30％草甘膦异丙胺盐水剂的用量为350g a.i/hm2。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例4
商品化Si-408对照，供试除草剂30％草甘膦异丙胺盐水剂的用量为350g a.i/hm2，选用商品化Si-408作为增效剂，添加量为喷洒药液质量的0.03％，测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例5
供试除草剂200g/L草铵膦水剂的用量为200g a.i/hm2，选用环境友好的聚乙二醇分子量为1000g/mol，氟醇为七氟丁醇的含氟非离子表面活性剂作为增效剂，其中200g/L草铵膦水剂喷洒液与环境友好含氟非离子表面活性剂的质量比为100∶0.005。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例6
供试除草剂50％草除灵水悬浮剂的用量为375g a.i/hm2，选用环境友好的聚乙二醇分子量为2000g/mol，氟醇为五氟丙醇的含氟非离子表面活性剂(作为增效剂，其中50％草除灵水悬浮剂喷洒液与环境友好含氟非离子表面活性剂的质量比为100∶0.01。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例7
供试除草剂50％丁草铵乳油的用量为500g a.i/hm2，选用环境友好的聚乙二醇分子量为2936g/mol，氟醇为十二氟庚醇的含氟非离子表面活性剂作为增效剂，其中50％丁草铵乳油喷洒液与环境友好含氟非离子表面活性剂的质量比为100∶0.1。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例8
供试除草剂80％敌草隆可湿性粉剂的用量为600g a.i/hm2，选用环境友好的聚乙二醇分子量为62g/mol，氟醇为2-氟乙醇的含氟非离子表面活性剂作为增效剂，其中80％敌草隆可湿性粉剂喷洒液与含氟非离子表面活性剂的质量比为100∶0.05。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例9
空白对照，不添加环境友好含氟非离子表面活性剂。供试除草剂200g/L草铵膦水剂的用量为200g a.i/hm2，50％草除灵水悬浮剂的用量为375g a.i/hm2，50％丁草铵乳油的用量为500g a.i/hm2，80％敌草隆可湿性粉剂的用量为600g a.i/hm2，测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例10
供试1％甲氨基阿维菌素苯甲酸盐乳油的用量为3g a.i/hm2，选用添加环境友好的聚乙二醇分子量为500g/mol，氟醇为十二氟庚醇的含氟非离子表面活性剂作为增效剂，其中1％甲氨基阿维菌素苯甲酸盐乳油喷洒液与添加环境友好含氟非离子表面活性剂的质量比为100∶0.05。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例11
供试1％甲氨基阿维菌素苯甲酸盐乳油的用量为3g a.i/hm2，选用添加环境友好的聚乙二醇分子量为2936g/mol，氟醇为九氟戊醇的含氟非离子表面活性剂作为增效剂，其中1％甲氨基阿维菌素苯甲酸盐乳油喷洒液与添加环境友好含氟非离子表面活性剂的质量比为100∶0.1。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例12
空白对照，不添加环境友好含氟非离子表面活性剂。供试1％甲氨基阿维菌素苯甲酸盐乳油的用量为3g a.i/hm2。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例13
商品化Si-408对照，供试1％甲氨基阿维菌素苯甲酸盐乳油的用量为3g a.i/hm2，选用商品化Si-408作为增效剂，添加量为喷洒药液质量的0.05％，测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例14
供试20％氯虫苯甲酰胺悬浮剂的用量为15g a.i/hm2，选用环境友好的聚乙二醇分子量为3890g/mol，氟醇为十二氟庚醇的含氟非离子表面活性剂作为增效剂，其中20％氯虫苯甲酰胺悬浮剂喷洒液与环境友好含氟非离子表面活性剂的质量比为100∶0.1。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例15
供试杀虫剂15％茚虫威水悬浮剂的用量为30g a.i/hm2，选用环境友好的聚乙二醇分子量为200g/mol，氟醇为七氟丁醇的含氟非离子表面活性剂作为增效剂，其中15％茚虫威水悬浮剂喷洒液与环境友好含氟非离子表面活性剂的重量比为100∶0.005。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例16
供试杀虫剂30％螺虫乙酯悬浮剂的用量为20g a.i/hm2，选用环境友好的聚乙二醇分子量为1000g/mol，氟醇为五氟丙醇的含氟非离子表面活性剂作为增效剂，其中30％螺虫乙酯悬浮剂喷洒液与环境友好含氟非离子表面活性剂的重量比为100∶0.02。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例17
供试杀虫剂5％氟虫腈悬浮种衣剂的用量为30g a.i/hm2，选用环境友好的聚乙二醇分子量为5078g/mol，氟醇为九氟戊醇的含氟非离子表面活性剂作为增效剂，其中5％氟虫腈悬浮种衣剂喷洒液与环境友好含氟非离子表面活性剂的重量比为100∶0.06。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例18
空白对照，不添加环境友好含氟非离子表面活性剂。供试20％氯虫苯甲酰胺悬浮剂的用量为15g a.i/hm2，15％茚虫威水悬浮剂的用量为30g a.i/hm2，30％螺虫乙酯悬浮剂的用量为20g a.i/hm2，5％氟虫腈悬浮种衣剂的用量为30g a.i/hm2。测量喷洒药液的静态表面张力、动态表面张力和接触角。
实施例19
将实施例10和实施例13的喷洒液分别室温放置一个月和54℃热储半个月，然后测量喷洒药液的静态表面张力、动态表面张力和接触角，与放置前进行比较。
实施例20
将实施例1、2、3和4进行室内活性测试。采用室内盆栽法，每个花盆中挑入20株稗草，加入药剂，注意保持稗草大小尽量一致，颜色鲜绿一致，并保持其完整性，在25℃培养观察，根据分级标准作好记录，根据稗草的受害情况进行评判药剂效果，计算EC50值(半最大效应浓度)。
实施例21
将实施例10、11、12和13进行室内活性测试。采用国际抗性行动委员会(IRAC)提出的喷雾法，用立式喷雾塔，喷雾量10ml，选取三龄小菜蛾幼虫，放入喷雾塔中进行制剂室内测定实验，每次使用试虫16头，每个浓度2次重复。48h后检查死亡率，计算LC50值(致死率为50％时的实际药液浓度)。
表1. 30％草甘膦异丙胺盐水剂稀释药液的静态表面张力
Figure BSA0000240702450000061
由表1可知，30％草甘膦异丙胺盐水剂稀释液的表面张力为45.03mN/m，当加入含氟非离子表面活性剂和Si-408后，表面张力明显下降。并且实施例1和实施例2的表面张力低于实施例4，说明含氟非离子表面活性剂的效果优于含硅表面活性剂Si-408。
表2. 30％草甘膦异丙胺盐水剂稀释药液的动态表面张力
Figure BSA0000240702450000062
由表2可知，当加入含氟非离子表面活性剂和Si-408后，在各个添加量下，表面张力的下降速度要明显优于无添加时。比较含氟非离子表面活性剂和Si-408，发现含氟非离子表面活性剂药液比Si-408药液的表面张力下降速度快。
表3. 30％草甘膦异丙胺盐水剂稀释药液的接触角
Figure BSA0000240702450000071
表4.除草剂(草铵膦、草除灵、丁草铵和敌草隆)稀释药液的静态表面张力
Figure BSA0000240702450000072
表5.除草剂(草铵膦、草除灵、丁草铵和敌草隆)稀释药液的动态表面张力
Figure BSA0000240702450000073
由表3可知，30％草甘膦异丙胺盐水剂稀释液在无添加任何表面活性剂的情况下，接触角为110.1°。当加入含氟非离子表面活性剂和Si-408后，药液在玉米叶片上接触角极大降低，表明含氟非离子表面活性剂和Si-408都能使药液的润湿性极大提升。比较含氟非离子表面活性剂和Si-408，含氟非离子表面活性剂的药液比含Si-408的药液在玉米叶片上接触角小，这说明所合成的环境友好含氟非离子表面活性剂对30％草甘膦异丙胺盐水剂200倍稀释液润湿性能的提升能力要略高于含硅表面活性剂Si-408。
表6.除草剂(草铵膦、草除灵、丁草铵和敌草隆)稀释药液的接触角
Figure BSA0000240702450000081
由表4、表5、表6可知，实施例5、6、7、8的静态表面张力、动态表面张力和接触角的值都低于不添加表面活性剂的稀释药液(实施例9)。
表7. 1％甲氨基阿维菌素苯甲酸盐乳油稀释药液的静态表面张力
Figure BSA0000240702450000082
由表7可知，1％甲维盐乳油稀释液的表面张力为36.94mN/m，当加入含氟非离子表面活性剂和Si-408后，表面张力明显下降。进一步比较含氟非离子表面活性剂和Si-408的降低表面张力的能力，发现所合成的环境友好含氟非离子表面活性剂的效果优于含硅表面活性剂Si-408。
表8. 1％甲氨基阿维菌素苯甲酸盐乳油稀释药液的动态表面张力
Figure BSA0000240702450000083
由表8可知，当加入含氟非离子表面活性剂和Si-408后，在各个添加量下，表面张力的下降速度要明显优于无添加时。例如，在1000ms时，无添加药液的表面张力仍为70mN/m左右，而对于含氟非离子表面活性剂和Si-408药液的表面张力已经低于50mN/m。比较含氟非离子表面活性剂和Si-408，发现所合成的环境友好含氟非离子表面活性剂药液比含Si-408药液的表面张力下降速度快。
表9. 1％甲氨基阿维菌素苯甲酸盐乳油稀释药液的接触角
Figure BSA0000240702450000091
表10.杀虫剂(氯虫苯甲酰胺、茚虫威、螺虫乙酯、氟虫腈)稀释药液的静态表面张力
Figure BSA0000240702450000092
表11.杀虫剂(氯虫苯甲酰胺、茚虫威、螺虫乙酯、氟虫腈)稀释药液的动态表面张力
Figure BSA0000240702450000093
由表9可知，1％甲维盐乳油稀释液在无添加任何表面活性剂的情况下，接触角为125.3°。当加入含氟非离子表面活性剂和Si-408后，药液在玉米叶片上接触角明显降低，表明含氟非离子表面活性剂和Si-408都能使药液的润湿性极大提升。比较含氟非离子表面活性剂和Si-408，发现所合成的环境友好含氟非离子表面活性剂对1％甲维盐乳油稀释液润湿性能的提升与含硅表面活性剂Si-408效果相当。
表12.杀虫剂(氯虫苯甲酰胺、茚虫威、螺虫乙酯、氟虫腈)稀释药液的接触角
Figure BSA0000240702450000101
由表10、表11、表12可知，实施例14、15、16、17的静态表面张力、动态表面张力和接触角的值都低于不添加表面活性剂的稀释药液(实施例18)。
表13.实施例19的表面张力数据
Figure BSA0000240702450000102
分析表13中数据，发现含Si-408稀释液放置前表面张力为28.01mN/m，室温放置一个月后表面张力升高到36.79mN/m，54℃热储半月后表面张力升高到39.43mN/m，说明Si-408在室温放置一个月后性能降低，有部分分解，而含氟非离子表面活性剂在室温放置前后的表面张力基本一样。综上所述，所合成的环境友好含氟非离子表面活性剂比Si-408在药液中稳定性好。
表14.实施例20的LC50值
Figure BSA0000240702450000103
表15.实施例21的LC50值
Figure BSA0000240702450000111
室内活性测试结果表明(表14和表15)：含所合成的环境友好含氟非离子表面活性剂药液的EC50和LC50值分别低于无添加药液的EC50和LC50值，这说明所合成的环境友好含氟非离子表面活性剂对除草剂和杀虫剂有增效作用。
综上所述，本发明提供的一种环境友好含氟非离子表面活性剂在实际应用中作为增效剂不仅能起到明显的增效作用，而且增效效果可以达到甚至超过商品化Si-408。并且相比于Si-408，可以使药液更持久的保持药效。

Claims (6)

1.一种环境友好含氟非离子表面活性剂作为增效剂在农药中的应用，所述环境友好含氟非离子表面活性剂结构式为：
Figure FSA0000240702440000011
式中R为CH3、
Figure FSA0000240702440000012
Rf为1～6个碳的氟烷基链，m整数，1≤m≤115。
2.根据权利要求1所述的环境友好含氟非离子表面活性剂作为增效剂在农药中的应用，其特征在于，可作为除草剂制剂的增效剂，其中环境友好含氟非离子表面活性剂与除草剂制剂的质量比为0.005～0.1∶100。
3.权利要求2所述的除草剂制剂的活性成分为草铵膦、草甘膦异丙胺盐、草除灵、丁草胺、敌草隆和苯磺隆中的一种。
4.根据权利要求1所述的环境友好含氟非离子表面活性剂作为增效剂在农药中的应用，其特征在于，可作为杀虫剂制剂的增效剂，其中环境友好含氟非离子表面活性剂与杀虫剂制剂的质量比为0.005～0.1∶100。
5.根据权利要求4所述的杀虫剂活性成分为茚虫威、氯虫苯甲酰胺、甲氨基阿维菌素苯甲酸盐、螺虫乙酯、氟虫腈和呋喃虫酰肼中的一种。
6.根据权利要求1～5所述环境友好含氟非离子表面活性剂作为增效剂在农药中的应用，其特征在于，其使用方法是在市售除草剂和杀虫剂稀释阶段添加环境友好含氟非离子表面活性剂进行混合使用。
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