CN108250245B - 纳米代森锰锌的制备方法 - Google Patents
纳米代森锰锌的制备方法 Download PDFInfo
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- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
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- A01N47/14—Di-thio analogues thereof
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Abstract
本发明公开了一种纳米级代森锰锌的制备方法,包括以下步骤:1)、制备代森锰:将代森铵、分散剂与缓冲液混合后,于30~50℃滴加锰盐水溶液;滴加完毕后,过滤,所得的滤饼Ⅰ干燥;2)、于40~50℃,在步骤1)所得的干燥后滤饼Ⅰ中加入水形成代森锰悬浊液,搅拌均匀,滴加锌盐水溶液,滴加完毕后过滤,所得的滤饼Ⅱ干燥,得到纳米级代森锰锌。本发明不经过物理研磨及其他工序,即可生产出纳米级别的代森锰锌。该纳米农药可以降低用药量,提高药效,且生产工艺环保简单。
Description
技术领域
本发明涉及一种杀菌剂-纳米级代森锰锌的制备方法。
背景技术
代森锰锌是一种优良的保护性杀菌剂,具有高效、低毒、广谱、抗性发展缓慢等特点,可防治多种果树、蔬菜的疫病、霜霉病、白粉病、炭疽病等真菌性病害,对柑橘黑点病(砂皮病)有特效。代森锰锌的全称是“乙撑双二硫代氨基甲酸锰锌络合物”,它是锌离子与代森锰颗粒表面形成的一种“表面络合物”,是代森锰与锌离子在颗粒表面局部化学反应的结果。非全络合态的代森锰锌因含有大量未络合的代森锰和少量的代森锰锌,既造成生产成本的浪费,又在杀菌过程中会快速释放过量的锰离子,对农作物产生极大地危害,间接伤害人和动物的身体健康,造成公害。因此,在生产过程中提高代森锰锌络合度至关重要。提高代森锰锌络合度的关键就是降低代森锰的粒径,锌离子就可以更好地与代森锰络合,生成全络合态代森锰锌。
专利CN 101962392 A公布了一种代森锰锌湿法研磨络合锌制备工艺,采用二级湿法研磨技术使代森锰颗粒足够小,从而与锌离子充分发生络合反应,得到全络合态的代森锰锌。此专利实际上是采用胶体磨和砂磨机研磨浆料,通过物理研磨降低代森锰锌颗粒粒径,粒径为2-5μm。但这样会造成生产能耗加大,不够环保。
专利CN 1695449A公布了一种代森锰锌制备工艺,将代森锰、锌盐、反应助剂打浆,然后把所得浆料置于研磨机内进行研磨,在研磨过程中物料发生络合反应得到全络合态代森锰锌,平均粒度小于5μm。和CN 101962392 A一样,也是通过物理研磨来降低产品粒径。
专利CN 104412999A公布了一种代森锰锌的配备方法,将代森锰与锌在有机溶剂中络合与脱水转晶,减少了产品的分解,降低了有害杂质和粉尘的污染,但该方法采用有机溶剂,而合成代森锰锌一般采用水作为溶剂,所以该发明实际上加重了污染。
目前国内外生产的代森锰锌制剂主要是可湿性粉剂和悬浮剂,可湿性粉剂采用代森锰锌原药加适当助剂、填料,通过机械粉碎加工而成的,平均粒径数十微米,在生产和应用过程中粉尘飞扬,不仅直接危害人畜健康,而且造成环境污染。为了克服可湿性粉剂的缺点,经改进形成了代森锰锌悬浮剂,把固态剂型再加工分散于水中形成液体制剂,平均粒径几个μm,但是也出现了容易分层、沉淀和结块的现象,包装量大,贮藏和运输不便。代森锰锌产品面临着进一步改进的需求。
专利CN 1545878A公布了一种代森锰锌水分散粒剂及其制造方法,由40-90%的代森锰锌加上润湿剂,分散剂,粘合剂,稳定剂和填料经加压喷雾干燥处理成空心球状颗粒。遇水能崩解分散成悬浮液,粒径在20-800μm左右。相比可湿性粉剂生产工艺,加工费用相对较高,工艺设备复杂。
专利CN 105104395A发明了一种90%代森锰锌微胶囊剂,以代森锰锌,分散剂为原料合成囊芯,然后直接加入囊材脲醛树脂进行剪切乳化,直接喷雾干燥法制得代森锰锌微胶囊剂。该微胶囊剂粒径在10μm左右,具有可控制释放,制备工艺简单的优点。但整个工艺中添加了脲醛树脂作为囊壳材料,不仅增大了生产成本,而且向环境中释放了更多的污染物。并且控制释放性能未加评估,药效也没有评估,存在一些问题。
综上所述,目前还没有一种生产工艺能直接制得粒径为1000nm以下的代森锰锌原药,而且大部分工艺是采用物理研磨的方法减小产品粒径,最细也在2μm左右。一些新的剂型,例如水分散粒剂,微胶囊剂,也存在着一些成本,环保等问题。
发明内容
本发明要解决的技术问题是提供一种纳米级(≤1000nm)代森锰锌及其制备方法。
为了解决上述技术问题,本发明提供一种纳米级代森锰锌的制备方法,包括以下步骤:
1)、制备代森锰:
将代森铵、分散剂(助剂)与缓冲液混合后,于30~50℃滴加锰盐水溶液;滴加(滴加时间为3~30分钟)完毕后,过滤,所得的滤饼Ⅰ(代森锰滤饼)干燥;
所述代森铵与锰盐的摩尔比为1:1~1.06,所述分散剂与代森铵的质量比为1:10~50(较佳为1:12~23);
2)、于40~50℃,在步骤1)所得的干燥后滤饼Ⅰ中加入水形成代森锰悬浊液,搅拌均匀,滴加锌盐水溶液,锌盐:锰盐=1:1的摩尔比;
滴加(滴加时间为3~30分钟)完毕后过滤,所得的滤饼Ⅱ干燥,得到纳米级代森锰锌(为黄绿色粉末状代森锰锌,粒径≤1000nm)。
作为本发明的纳米级代森锰锌的制备方法的改进:
所述锰盐为硫酸锰(优选)、醋酸锰、氯化锰、硝酸锰;
所述锌盐为硫酸锌(优选)、醋酸锌、氯化锌、硝酸锌。
作为本发明的纳米级代森锰锌的制备方法的进一步改进:
所述分散剂是木质素磺酸钙、木质素磺酸钠、木质素硅酸钠、木质素三聚磷酸钠、苯乙基酚聚氧乙烯醚硫酸钠、萘磺酸甲醛缩合物钠盐(优选)、扩散剂D-450中的至少一种(即,为任意一种,或采取以上两种或两种以上物质的混合物)。
作为本发明的纳米级代森锰锌的制备方法的进一步改进:
所述缓冲液为pH=6的磷酸盐缓冲液。
作为本发明的纳米级代森锰锌的制备方法的进一步改进:
所述步骤1)中,锰盐水溶液的浓度为1~1.5mol/L(较佳为1.16mol/L);
所述步骤2)中,锌盐水溶液的浓度为1~1.5mol/L(较佳为1.16mol/L)。
在本发明中:每5.5~80mmol的代森铵,步骤2)中加入20~40ml水从而形成代森锰悬浊液。步骤1)干燥后的滤饼Ⅰ为代森锰,直径优选为400~500nm;步骤2)所得的纳米级代森锰锌粒径优选为400~500nm。
本发明在制备代森锰时,加入pH=6的磷酸盐缓冲液和分散剂,使代森锰的粒径降低,再与锌离子络合,从而实现不用研磨等物理方法就能降低产物的粒径。
即,本发明是采用化学的方法,从代森锰锌合成的关键中间体代森锰出发,通过合成工艺参数的改变与优化,在关键反应步骤中加入合适的助剂(分散剂),制得纳米级代森锰锌原药。制备的代森锰颗粒小,从而使其与锌离子充分发生络合反应,得到全络合态的代森锰锌。
本发明不经过物理研磨及其他工序,即可生产出纳米级别的代森锰锌。该纳米农药不仅可以降低用药量,提高药效,生产工艺环保简单,在使用经济上也得到突破制备方法独特,在生产过程和应用过程中可大大降低用药量,减少成本。
综上所述,采用本发明的工艺制备的代森锰颗粒小,从而使其能与锌离子充分发生络合反应,得到粒度为400-500nm的全络合态代森锰锌。该纳米代森锰锌直接加水稀释使用,不仅可以降低用药量,提高药效,在使用经济性上也得到突破。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细说明。
图1为是纳米代森锰锌(实施例1制备而得)的粒径分布图;
图2为纳米代森锰锌(实施例1制备而得)的扫描电镜图;
图3为80%代森锰锌可湿性粉剂(陶氏绿大生)的扫描电镜图;
图4为不同粒径代森锰锌分散于水中,静置一天后的分散性图;
图4中,从左至右依次为500nm代森锰锌(左)、西安近代代森锰锌原药(中)、10μm代森锰锌(右)。
具体实施方式
下面具体的实施例来详细说明本发明纳米代森锰锌的制备方法、思路途径,所述实施例是为了更好的解释本发明,而不是对发明权利要求保护范围的限制,所有基于本发明基本思想的修改和变动,都属于本发明请求保护的范围。
称取乙二胺5.00g(83mmol)加入10ml水中,30-40℃搅拌下,滴加12.67g二硫化碳(166mmol),滴加完毕(滴加时间为20-30min)后,继续滴加12.47g氨水(25%,186mmol),滴加完毕(滴加时间为5-10min)后,继续搅拌1h,TLC显示乙二胺反应完毕,体系变成澄清的橙黄色溶液---代森铵水溶液(代森铵浓度为2.05g/ml)
以下案例所采用的代森铵均指采用上述方法得到的代森铵水溶液,且下文中所指为代森铵的有效重量。
实施例1:
1)、称取代森铵1.36g(5.5mmol),加入分散剂萘磺酸甲醛缩合物钠盐70mg,pH=6的磷酸盐缓冲液20mL,40℃下,3min滴加5mL(1.16mol/L)一水合硫酸锰溶液,滴加完毕过滤,所得的滤饼Ⅰ干燥(60℃干燥至恒重);
2)、将在步骤1)所得的干燥后滤饼Ⅰ中加入20mL水形成代森锰悬浊液;40℃下,3min滴加5mL(1.16mol/L)七水合硫酸锌溶液,滴加完毕后过滤,所得的滤饼Ⅱ干燥(60℃干燥至恒重),得到黄绿色代森锰锌粉末。
如图1所示,使用马尔文粒度测定仪测定代森锰锌粒度为430nm。进一步通过扫描电镜(SEM)分析,如图2所示,纳米代森锰锌的粒径范围约为400-500nm左右。以下为方便描述,简称为500nm样品。
实施例2:
1)、取5.0g(0.02mol)代森铵溶于pH=6的磷酸盐缓冲液20mL中,加入400mg木质木质素磺酸钠,50℃下搅拌。7min滴加18mL(1.16mol/L)一水合硫酸锰溶液,体系呈土黄色浑浊液体,滴加完毕,过滤,所得的滤饼Ⅰ干燥;
2)、向步骤1)所得的干燥后滤饼Ⅰ,加入25mL水,搅拌形成悬浊液。40℃下,7min滴加18mL(1.16mol/L)七水合硫酸锌溶液,滴加完毕后过滤,所得的滤饼Ⅱ干燥,得到黄绿色代森锰锌粉末。
使用扫描电镜测定代森锰锌粒度为500-600nm。
实施例3:
1)、取5.7g(0.023mol)代森铵溶于pH=6的磷酸缓冲盐30mL中,加入250mg分散剂NNO,50℃搅拌。15min滴加20mL(1.16mol/L)一水合硫酸锰,滴加完毕,过滤,所得的滤饼Ⅰ干燥;
2)、向步骤1)所得的干燥后滤饼Ⅰ,加入30mL水,搅拌形成悬浊液。40℃下,15min滴加20mL(1.16mol/L)七水合硫酸锌溶液,滴加完毕后过滤,所得的滤饼Ⅱ干燥,得到黄绿色代森锰锌粉末。
使用扫描电镜测定代森锰锌粒度为500-600nm。
实施例4:
1)、取20.0g(0.08mol)代森铵溶于pH=6的磷酸缓冲盐50mL中,加入1.0g木质素硅酸钠,50℃搅拌。30min滴加70mL(1.16mol/L)一水合硫酸锰溶液,滴加完毕,过滤,所得的滤饼Ⅰ干燥;
2)、向步骤1)所得的干燥后滤饼Ⅰ,后加入40mL水,搅拌形成悬浊液。40℃下,30min滴加70mL(1.16mol/L)七水合硫酸锌,滴加完毕过滤干燥得到黄绿色代森锰锌粉末。
使用扫描电镜测定代森锰锌粒度为500-600nm。
对比例1、
将实施例1中的pH=6的磷酸盐缓冲液换成pH=8的磷酸盐缓冲液,体积量不变;其余等同于实施例1。
使用扫描电镜测定代森锰锌粒度为8-10μm。以下为方便描述,简称为10μm样品。
实验一:
称取500nm代森锰锌(实施例1所得),10μm代森锰锌(对比例1所得),西安近代代森锰锌原药各100mg,加入适量水,搅拌均均,然后用纯净水定容至100mL,静置1天。结果表明,自制的500nm代森锰锌,10μm代森锰锌分散均匀,而西安近代原药大部分沉积在底部,无法很好分散。如图4所示。
进一步验证了采用本发明方法得到的代森锰锌分散性能优越,具有实际的应用价值。
实验二、代森锰锌生物活性测定:
制备的纳米代森锰锌可以加工成可分散于水中的农化制剂。例如纳米代森锰锌水基悬浮剂或水分散粒剂或其他分散于水中的可湿性粉剂、颗粒剂等。用于生物测定选择纳米代森锰锌直接加水稀释,形成悬浮液;用孢子萌发法进行抑菌活性生物测定。称取供试药剂A、B、C、D各100mg,分散于5mL水中配成一定浓度的母液,并依次用水稀释成系列浓度的母液稀释液,取50μL的相应浓度的母液或稀释液加入50mL温热的WA(水琼脂培养基)培养基,配成系列浓度的含药平板。在预实验的基础上,设置8个浓度,依次为:0、0.25、0.35、0.5、0.7、1.0、1.4和2.0μg/mL。分别取随机选取的柑橘黑点病菌(Diaporthe citri)12个菌株的新鲜分生孢子于无菌水中配成105个/mL的孢子悬浮液,均匀涂布于含不同药剂浓度的WA培养基平板上。26℃黑暗条件下倒置培养14h后,在光学显微镜下观察并记录萌发及未萌发的孢子数,以芽管长度超过孢子宽度视为萌发,因β型分生孢子不会萌发,只记录α型分生孢子的萌发情况。每菌株每个浓度重复三次,每个重复观察的孢子总数不低于200个。计算各菌株各浓度下孢子萌发抑制率,将数据输入IBM SPSS19.0统计软件,运用probit模块得到一条以药剂浓度10为底的对数为横坐标,常态等差为纵坐标的拟合直线,得到EC50,EC95值,结果如下表1。
表1、4种代森锰锌原药对柑橘黑点病病原菌孢子萌发的毒力测定
从表中可以看出,500nm代森锰锌原药EC50和EC95均低于对照药剂80%西安近代WP和80%陶氏绿大生WP,10μm代森锰锌原药EC50和EC95低于80%西安近代WP,高于80%陶氏绿大生WP。而且500nm代森锰锌直接加入水中搅拌分散均匀后即可用于生测,不用添加分散剂等助剂,使用方便。使用本发明方法制备的500纳米级代森锰锌具有高络合度,杀菌性能优异的特点,具有较好的社会效益和经济效益。
实施例2、将实施例1中的一水合硫酸锰溶液分别改成:醋酸锰溶液、氯化锰溶液、硝酸锰溶液;浓度和体积量均不变,其余等同于实施例1。
对比例2-1、取消实施例1中分散剂萘磺酸甲醛缩合物钠盐70mg的使用,其余等同于实施例1。
对比例2-2、将实施例1中作为分散剂的萘磺酸甲醛缩合物钠盐的用量由70mg改成0.4g,其余等同于实施例1。
对比例3、将实施例1步骤1)的滴加一水合硫酸锰溶液改成将直接将一水合硫酸锰溶液一次性加入完毕后,搅拌反应3min,其余等同于实施例1。
对比例4、取消实施例1步骤1)中分散剂萘磺酸甲醛缩合物钠盐70mg的使用,且在步骤2)中的代森锰悬浊液中加入分散剂萘磺酸甲醛缩合物钠盐70mg;其余等同于实施例1。
将上述所有的案例按照上述实验一、实验二所述方法进行检测,所得结果如下表2所示。
表2
最后,还需要注意的是,以上列举的仅是本发明的若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (3)
1.纳米级代森锰锌的制备方法,其特征是包括以下步骤:
1)、制备代森锰:
将代森铵、分散剂与缓冲液混合后,于30~50℃滴加锰盐水溶液;滴加完毕后,过滤,所得的滤饼Ⅰ干燥;
所述代森铵与锰盐的摩尔比为1:1~1.06,所述分散剂与代森铵的质量比为1:12~23;
所述缓冲液为pH=6的磷酸盐缓冲液;
所述锰盐为硫酸锰、醋酸锰、氯化锰、硝酸锰;
所述分散剂是木质素磺酸钙、木质素磺酸钠、木质素硅酸钠、木质素三聚磷酸钠、苯乙基酚聚氧乙烯醚硫酸钠、萘磺酸甲醛缩合物钠盐、扩散剂D-450中的至少一种;
2)、于40~50℃,在步骤1)所得的干燥后滤饼Ⅰ中加入水形成代森锰悬浊液,搅拌均匀,滴加锌盐水溶液,锌盐:锰盐=1:1的摩尔比;
所述锌盐为硫酸锌、醋酸锌、氯化锌、硝酸锌;
滴加完毕后过滤,所得的滤饼Ⅱ干燥,得到纳米级代森锰锌。
2.根据权利要求1所述的纳米级代森锰锌的制备方法,其特征是:
所述步骤1)的滴加时间为3~30分钟,所述步骤2)的滴加时间为3~30分钟。
3.根据权利要求2所述的纳米级代森锰锌的制备方法,其特征是:
所述步骤1)中,锰盐水溶液的浓度为1~1.5 mol/L;
所述步骤2)中,锌盐水溶液的浓度为1~1.5 mol/L。
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