CN111363180A - 一种基于金属骨架材料的农药吸附可降解复合膜及其制备方法 - Google Patents
一种基于金属骨架材料的农药吸附可降解复合膜及其制备方法 Download PDFInfo
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Abstract
本发明属于新型农用薄膜材料领域,具体提供了一种基于金属骨架材料的农药吸附可降解复合膜及其制备方法,该可降解复合膜利用金属骨架材料MOF‑5作为农药的吸附载体、以聚乙烯醇、淀粉制备的复合膜作为基质、通过静电喷雾技术使载有农药的金属‑有机骨架材料吸附于可降解复合膜表面,能够起到保墒、增温、抑制杂草等作用,对未来绿色农业的发展具有重要且深远的意义。
Description
技术领域
本发明属于新型农用薄膜材料领域,具体涉及一种基于金属骨架材料的农药吸附可降解复合膜及其制备方法。
技术背景
目前,在农业生产中农膜、农药的使用实现了农业生产力的飞跃和生产方式的改变。但是传统农膜的化学成分主要是聚乙烯或聚氯乙烯,自然条件下无法在土壤中降解,长期残留的农膜老化变硬,会破坏耕作层的土壤结构,阻隔土壤水肥传导,降低土壤微生物的活动能力,使土壤抗旱能力下降,对土地生产能力和农业可持续发展造成不良影响。
为降低农药直接接触土壤对环境造成不良影响,多种类型的缓释膜应运而生,如选用聚乙烯醇和淀粉的共混物为膜原料,埃洛石纳米管和蒙脱土等为药物载体制备农药缓释膜。多种缓释膜的研究有助于提高农药的利用率一定程度减少农药对于土地的破坏。
金属有机框架化合物(Metal Organic Frameworks,MOFs)是由无机金属离子组成的次级结构单元和含氧或氮的有机配体通过强化学键连接在一起而形成的具有三维周期性网状结构的多孔配位聚合物材料。由于其化学组分的特性,MOFs材料同时具备有机材料与无机材料的性能。MOFs材料具有高比表面积、高孔隙率以及优异的热稳定性能,且其结构可通过拓扑结构定向设计和有机官能团的拓展进行调控和设计。因此,MOFs材料在气体分离、储能、催化、吸附等领域得到了广泛的关注与应用。由于分子孔道内部具有丰富的活性位点,近年来,MOFs材料在吸附领域的研究与应用与日俱增。但有关MOFs材料对农药分子吸附的研究仍鲜有报道。
静电喷雾方法是静电纺丝的一种,原理是基于电-流体力学工作原理,可以使用聚合物熔体或聚合物溶液进行;相比之下,由于没有有机溶剂和工艺简单,静电喷雾更经济、更环保。静电喷雾已被研究并应用于生物医学工程中的几个应用领域,如药物传递、生物传感器、组织工程和再生医学。
综上所述,在传统农膜、农药的应用方面存在两个亟待解决的问题:(1)传统农膜不可降解,残膜存留在土壤中还会阻碍农作物生长,影响作物养分和水分的吸收,降低作物产量;(2)没有合适的吸附材料,控制农药的释放。因此如何综合上述现有技术来解决上述问题成为本领域的难题。
发明内容
本发明针对现有技术存在的诸多不足之处,提供了一种基于金属骨架材料的农药吸附可降解复合膜及其制备方法,该可降解复合膜利用金属骨架材料MOF-5纳米颗粒作为农药的吸附载体、以聚乙烯醇、淀粉制备的复合膜作为基质、通过静电喷雾技术使载有农药的金属-有机骨架材料吸附于可降解复合膜表面,能够起到保墒、增温、抑制杂草等作用,对未来绿色农业的发展具有重要且深远的意义。
本发明的具体技术方案是:
一种基于金属-有机骨架材料的农药吸附可降解复合膜,其由可降解生物膜和吸附于可降解生物膜表面的载药金属-有机骨架材料组成;
所述的金属-有机骨架材料为MOF-5纳米颗粒;
所述的载药金属-有机骨架材料通过静电喷雾技术吸附于可降解生物膜表面;
所述的金属-有机骨架材料为MOF-5纳米颗粒,其具体制备方法如下:原料组成按照重量份计为:
无水醋酸锌3-4份、对苯二甲酸1份、DMF 10-15份;
将无水醋酸锌、对苯二甲酸在DMF中超声震荡仪中分散10-15min,控制温度为20-25℃;
将所得的混合溶液移入洁净的内壁带有聚四氟涂层的反应釜中;
将反应釜温度控制在120℃下反应24-30h;
将所得的反应物于5800-6800rpm下离心10min,并用DMF洗涤离心产物3-5次;
将离心后的产物置于真空干燥器中干燥12-14h,即得MOF-5纳米颗粒;
上述的溶剂热反应,其选用的溶剂为DMF,可使MOF-5纳米颗粒结晶度较好,粒径更加均匀,可获得纳米级MOF-5,其粒径范围经检测为5nm-12nm。
所述的载药MOF-5制备方法如下:
所选的农药为三嗪类除草剂中的一种,为避免所选MOF-5纳米颗粒吸附溶剂分子,导致负载量下降,所使用的溶剂均为氯仿,下面以阿特拉津为例,也可以选用其他三嗪类除草剂;
将20g制备获得的MOF-5纳米颗粒分散于浓度为0.006g/L-0.03g/L的阿特拉津/氯仿溶液中;
将混合溶液置于恒温震荡培养箱中,控制温度在30℃-65℃,吸附时间为24h-72h;
将上述所得的混合物反应物于5800-6800rpm下离心10-15min,所得产物干燥24h,得到载药MOF-5纳米颗粒,经检测计算颗粒中的阿特拉津负载量为0.05-0.08phr。
上述的可降解生物膜由聚乙烯醇、淀粉为主要原料制备而成,其原料组成按重量份计为:
聚乙烯醇65-75份、淀粉15-20份、增塑剂5-10份、相容剂5-10份;
其中所述的增塑剂为甘油,聚乙二醇,季戊四醇,木糖醇,甘露醇,1,2,6-己三醇,1,4-丁二醇中的一种或多种,相容剂为柠檬酸、氢氧化铝中的一种或多种。
其具体制备方法如下:
按照上述组成称取原料,将聚乙烯醇与淀粉、增塑剂,相容剂在高速搅拌机,控制转速为8000-10000rpm中混合10-15分钟;
将所得的混合物体系在温度120℃-150℃条件下用螺杆挤出机直接共混挤出造粒,得聚乙烯醇/淀粉复合材料;
将聚乙烯醇/淀粉复合材料经挤出吹膜制成30-40um的可降解生物膜。
在获得了上述的可降解生物膜之后,发明人进一步提供了将载药MOF-5纳米颗粒吸附于可降解生物膜表面的具体工艺如下:
配备喷雾原液:将载药MOF-5纳米颗粒按照质量分数10-15%,分散于甲醇中,利用超声分散,控制温度为20-25℃,分散时间为6-8h,获得喷雾原液;
选用TYD01静电喷雾仪,调配TYD01静电喷雾仪工艺参数:喷雾条件控制在温度25℃-35℃,喷雾电压10-15kv,喷雾溶液流速为1-10ml,喷雾接收距离10-15cm,接收棍电极转速500-1000rpm,针头来回走速30-50cm/min,喷雾时间为24h-36h;
将可降解生物膜固定于TYD01静电喷雾仪载物电极板上,将载物电极板与正极线相连,按照上述操作参数对其进行喷雾;
将获得的载药后的可降解生物膜在自然条件下干燥,即得分布均匀的农药缓释膜。
与现有技术相比,本发明的优点在于:
(1)本发明所采用的的可降解生物膜的主要成分为聚乙烯醇与淀粉,聚乙烯醇(PVA)薄膜具有水溶性、可降解性等方面的独特优点,淀粉是来源广泛、价格便宜的天然高分子材料;将淀粉添加到聚乙烯醇中不仅可以大大降低成本,还可以促进薄膜的生物降解,提高了薄膜的可降解性能。
(2)本发明所采用的吸附材料为金属-有机框架化合物MOF-5纳米颗粒,该种材料孔径大,吸附性能好,能够将农药有效的吸附进孔径内,降低农药对土壤的直接危害,较之现有的农药缓释膜有较大的进步。
(3)本发明所采用的静电喷雾技术将载药MOF-5纳米颗粒吸附于可降解生物膜基质表面不会对膜的结构稳定性造成影响。
(4)本发明所得的农药缓释膜较之传统农药缓释膜,选用的吸附剂为金属-有机骨架材料,其结构在15-45天内塌陷,随之持续释放所负载的农药,最终MOF-5纳米颗粒结构塌陷所得的分解的产物含有锌元素有益于农作物生长。
具体实施方式
下面对本发明的较佳实施例进行详细阐述,以使本发明的优点和特征能更易于被本领域技术人员理解,从而对本发明的保护范围做出更为清楚明确的界定,除特殊说明外,所采用的均为现有技术;
实施例1
一种基于金属-有机骨架材料的农药吸附可降解复合膜,其由可降解生物膜和吸附于可降解生物膜表面的载药金属-有机骨架材料组成;
其中金属-有机骨架材料的制备:
(1)称量66g无水醋酸锌、20g对苯二甲酸,
量取DMF200g,将无水醋酸锌、对苯二甲酸在DMF中超声震荡仪中分散10min,控制温度为25℃;
(2)将所得的混合溶液移入洁净的内壁有聚四氟乙烯的反应釜中;
(3)将反应釜置于烤箱中在120℃情况下反应24h;
(4)将所得的反应物于5800rpm下离心10min,并用DMF重复洗涤3次;
(5)将离心后的产物置于真空干燥器中干燥12h,即得MOF-5纳米颗粒,其粒径范围为5nm-12nm。
可降解生物膜的制备:
(1)称量聚乙烯醇65g、淀粉15g、甘油5g、柠檬酸5g;
(2)将聚乙烯醇与淀粉、甘油、柠檬酸在高速搅拌机以10000rpm转速混合10分钟;
(3)将所得的混合物体系在温度125℃条件下用螺杆挤出机直接共混挤出造粒,得聚乙烯醇/淀粉复合材料;
(4)将聚乙烯醇/淀粉复合材料经挤出吹膜制成40um的可降解生物膜。
载药MOF-5纳米颗粒的制备:
(1)称量20gMOF-5,量取300ml浓度为0.03g/L的阿特拉津/氯仿溶液;
(2)将20gMOF-5分散于上述浓度为0.03g/L的阿特拉津/氯仿溶液中;
(3)将混合溶液置于恒温震荡培养箱中,控制温度在35℃,吸附时间为36h;
(4)将上述所得的混合物于5800rpm下离心10min;
(5)所得产物干燥24h,得到载药MOF-5纳米颗粒,所得颗粒中阿特拉津的负载量为0.08phr。
使用静电喷雾方法制备农药缓释膜:
(1)配备喷雾原液:称取20g上述获得的载药MOF-5纳米颗粒利用超声分散,控制温度为25℃,分散于200g甲醇中,获得喷雾原液,分散时间为6h;
(2)调配TYD01静电喷雾仪工艺参数:喷雾条件控制在温度30℃,喷雾电压12kv,喷雾溶液流速为8μL/min,喷雾接收距离10-15cm,接收棍电极转速800rpm,针头来回走速35cm/min,喷雾时间为24h;
(3)将可降解生物膜固定于TYD01静电喷雾仪载物电极板上,将载物电极板与正极线相连,按照上述操作参数对其进行喷雾;
(4)自然条件下干燥,即得分布均匀的农药缓释膜。
经检测膜的拉该方法制得的农药缓释膜的拉伸强度28.5MPa,断裂伸长率为356%,膜厚40um,在45d内生物降解率为52%,农药释放比为75.6%。
对比例1
本对比例与实例1的区别在于省去制备载药MOF-5纳米颗粒材料,使用静电喷雾方法制备农药缓释膜时将载药金属-有机框架MOF-5纳米颗粒替换为农药,其余步骤均相同。
经检测膜的拉该方法制得的农药缓释膜的拉伸强度29.5MPa,断裂伸长率为372%,膜厚37um,5d内农药释放比100%,在45d内生物降解率为49%。
对比例2
本对比例与实例1的区别在于省去制备载药MOF-5纳米颗粒材料,使用静电喷雾方法制备农药缓释膜时将载药金属-有机框架MOF-5纳米颗粒替换为MOF-5纳米颗粒,其余步骤均相同。
经检测膜的拉该方法制得的农药缓释膜的拉伸强度28.5MPa,断裂伸长率为364%,膜厚35um,在45d内生物降解率为51%。
实施例2
一种基于金属-有机骨架材料的农药吸附可降解复合膜,其由可降解生物膜和吸附于可降解生物膜表面的载药金属-有机骨架材料组成;
其中金属-有机骨架材料的制备:
(1)称量40g无水醋酸锌、20g对苯二甲酸,
(2)量取DMF200g,将无水醋酸锌、对苯二甲酸在DMF中超声震荡仪中分散10min,控制温度为20℃;
(3)将所得的混合溶液移入洁净的带有聚四氟乙烯的反应釜中;
(4)将反应釜置于烤箱中在120℃情况下反应24h;
(5)将所得的反应物于6800rpm下离心10min,并用DMF重复洗涤3次;
(6)将离心后的产物置于真空干燥器中干燥14h,即得MOF-5,其粒径范围为4nm-8nm。
制备可降解生物膜:
(1)称量聚乙烯醇60g、淀粉20g、甘油5g、柠檬酸5g;
(2)将聚乙烯醇与淀粉、甘油、柠檬酸在高速搅拌机中混合10分钟;
(3)将所得的混合物体系在温度135℃条件下用螺杆挤出机直接共混挤出造粒,得聚乙烯醇/淀粉复合材料;
(4)将聚乙烯醇/淀粉复合材料经挤出吹膜制成36um的可降解生物膜。
制备载药MOF-5纳米颗粒材料:
(1)称量20gMOF-5纳米颗粒,量取300ml浓度为0.02g/L的阿特拉津/氯仿溶液;
(2)将20gMOF-5纳米颗粒分散于上述浓度为0.02g/L的阿特拉津/氯仿溶液中;
(3)将混合溶液置于恒温震荡培养箱中,控制温度在25℃,吸附时间为48h;
(4)将上述所得的混合物于6800rpm下离心15min;
(5)所得产物干燥24h,得到载药MOF-5纳米颗粒,所得颗粒负载量为0.075phr。
使用静电喷雾方法制备农药缓释膜:
(1)配备喷雾原液:称取20g上述获得的载药MOF-5纳米颗粒超声分散,控制温度为20℃于200g甲醇中,获得喷雾原液,分散时间为8h;
(2)调配TYD01静电喷雾仪工艺参数:喷雾条件控制在温度30℃,喷雾电压12kv,喷雾溶液流速为8μL/min,喷雾接收距离15cm,接收棍电极转速800rpm,针头来回走速35cm/min,喷雾时间为24h;
(3)自然条件下干燥,即得分布均匀的农药缓释膜。
经检测膜的拉该方法制得的农药缓释膜的拉伸强度28.5MPa,断裂伸长率为298%,膜厚36um,在45d内生物降解率为58%,农药释放比为83.3%。
实施例3
一种基于金属-有机骨架材料的农药吸附可降解复合膜,其由可降解生物膜和吸附于可降解生物膜表面的载药金属-有机骨架材料组成;
其中金属-有机骨架材料的制备:
(1)称量45g无水醋酸锌、15g对苯二甲酸,
(2)量取DMF150g,将无水醋酸锌、对苯二甲酸在DMF中超声震荡仪中分散10min;
(3)将所得的混合溶液移入洁净的带有聚四氟乙烯的反应釜中;
(4)将反应釜置于烤箱中在120℃情况下反应30h;
(5)将所得的反应物于6500rpm下离心10min,并用DMF重复洗涤3次;
(6)将离心后的产物置于真空干燥器中干燥12h,即得MOF-5纳米颗粒,其粒径范围为5nm-10nm。
制备可降解生物膜:
(1)称量聚乙烯醇50g、淀粉30g、甘油5g、柠檬酸5g;
(2)将聚乙烯醇与淀粉、甘油、柠檬酸在高速搅拌机中混合10分钟;
(3)将所得的混合物体系在温度120℃条件下用螺杆挤出机直接共混挤出造粒,得聚乙烯醇/淀粉复合材料;
(4)将聚乙烯醇/淀粉复合材料经挤出吹膜制成37um的可降解生物膜。
制备载药MOF-5纳米颗粒材料:
(1)称量20gMOF-5纳米颗粒,量取30ml浓度为0.01g/L的阿特拉津/氯仿溶液;
(2)将20gMOF-5纳米颗粒分散于上述浓度为0.01g/L的阿特拉津/氯仿溶液中;
(3)将混合溶液置于恒温震荡培养箱中,控制温度在35℃,吸附时间为36h;
(4)将上述所得的混合物于5800rpm下离心10min;
(5)所得产物干燥24h,得到载药MOF-5纳米颗粒,其颗粒负载量为0.05phr。
使用静电喷雾方法制备农药缓释膜:
(1)配备喷雾原液:称取20g上述获得的载药MOF-5纳米颗粒分散于200g甲醇中,获得喷雾原液,分散时间为12h;
(2)调配TYD01静电喷雾仪工艺参数:喷雾条件控制在温度30℃,喷雾电压12kv,喷雾溶液流速为8μL/min,喷雾接收距离15cm,接收棍电极转速800rpm,针头来回走速35cm/min,喷雾时间为24h;
(3)自然条件下干燥,即得分布均匀的农药缓释膜。
经检测膜的拉该方法制得的农药缓释膜的拉伸强度25.5MPa,断裂伸长率为253%,膜厚37um,在45d内生物降解率为63%,农药释放比为82.8%。
上述实施例和对比例中生物降解率和农药释放比的相关实验测试方法如下:
10L的容器,充满泥土(从养殖场获得),15片3*10mm的薄膜埋在10厘米深的土里,容器放置在自然条件下,土壤保持湿润,定期间隔洒水,保持20-40%湿度。多余的水从锅底的洞里流出来。通过在定期的时间间隔(15天)从土壤中小心地取出试样,并用蒸馏水轻轻清洗以除去土壤,测定试样的降解度,试样在真空下干燥,直到得到恒定的重量。用试样随时间的变化而失重来指示降解速率。
将20g样品放入透析袋中,用绳栓封口放于装有200ml去离子水的500mL烧杯中,按照拟定时间取样(见表1),更换200mL去离子水。用液相色谱等仪器对样品进行检测其有效成分含量,统计样品的释放比。
统计公式:
其中W%-降解率
W0-原始重量
W1-样品测定重量
S%=100%×∑(CV)/M
其中:S-释放百分比
M-样品中农药有效成分总质量
V-每次取样体积,100mL:
C每次取样的农药有效成分浓度
实验结果如下表:
表一:基于金属-有机骨架材料的农药吸附可降解复合膜农药释放比
表二:基于金属-有机骨架材料的农药吸附可降解复合膜降解率
由上述数据可知实施例1、2、3与对比例1,2相比,载药MOF-5纳米颗粒作用于可降解复合膜与单一组分作用于可降解复合膜对膜的降解性能无影响,农药吸附可降解复合膜与无载体的农药膜相比可有效控制药物释放。在15d后,基于金属-有机骨架材料的农药吸附可降解复合膜对于农药的释放涉及金属-有机骨架材料结构的塌陷导致吸附于金属-有机骨架材料中的农药进一步释放,控制了农药的释放比。对于可降解复合膜对膜的降解性能而言,可降解复合膜中淀粉与聚乙烯醇的比例可影响膜的生物降解性,淀粉的含量可提高膜的生物降解性。
Claims (7)
1.一种基于金属骨架材料的农药吸附可降解复合膜,其特征在于:其由可降解生物膜以及吸附于可降解生物膜表面的载药金属-有机骨架材料组成;
其中所述金属-有机骨架材料为MOF-5纳米颗粒;
所述可降解复合膜由聚乙烯醇、淀粉制备而成;通过静电喷雾技术将载药金属-有机骨架材料吸附于可降解复合膜表面。
2.根据权利要求1所述基于金属骨架材料的农药吸附可降解复合膜,其特征在于:所述MOF-5的原料组成按照重量份计为:
无水醋酸锌3-4份、对苯二甲酸1份、DMF 10-15份。
3.根据权利要求1所述基于金属骨架材料的农药吸附可降解复合膜,其特征在于:所述可降解复合膜原料组成按重量份计为:
聚乙烯醇65-75份、淀粉15-20份、增塑剂5-10份、相容剂5-10份;
其中所述的增塑剂为甘油,聚乙二醇,季戊四醇,木糖醇,甘露醇,1,2,6-己三醇,1,4-丁二醇中的一种或多种,相容剂为柠檬酸、氢氧化铝中的一种或两种。
4.根据权利要求2所述基于金属骨架材料的农药吸附可降解复合膜,其特征在于:所述MOF-5的制备方法如下:
将无水醋酸锌、对苯二甲酸在DMF中超声震荡仪中分散10-15min,控制温度为20-25℃;
将所得的混合溶液移入洁净的内壁带有聚四氟涂层的反应釜中;
将反应釜温度控制在120-140℃下反应24-30h;
将所得的反应物于5800-6800rpm下离心10-15min,并用DMF洗涤离心产物3-5次;
将离心后的产物置于真空干燥器中干燥12-14h,即得MOF-5纳米颗粒,其粒径范围为5nm-12nm。
5.根据权利要求4所述基于金属骨架材料的农药吸附可降解复合膜,其特征在于:所述的载药MOF-5纳米颗粒制备方法如下:
将MOF-5纳米颗粒分散于浓度为0.006g/L-0.03g/L的三嗪类除草剂/氯仿溶液中;
将混合溶液置于恒温震荡培养箱中,控制温度在30℃-65℃,吸附时间为24h-72h;
将上述所得的混合物反应物于5800-6800rpm下离心10-15min,所得产物干燥24h,得到载药MOF-5纳米颗粒,颗粒负载量为0.05-0.08phr;
其中所述的农药为三嗪类除草剂,选自但不限于阿特拉津。
6.根据权利要求3所述基于金属骨架材料的农药吸附可降解复合膜,其特征在于:所述可降解复合膜的制备方法如下:
按照组成称取原料,将聚乙烯醇与淀粉、增塑剂,相容剂在高速搅拌机中,控制转速为8000-10000rpm混合10-15分钟;
将所得的混合物体系在温度120℃-150℃条件下用螺杆挤出机直接共混挤出造粒,得聚乙烯醇/淀粉复合材料;
将聚乙烯醇/淀粉复合材料经挤出吹膜制成30-40um的可降解生物膜。
7.权利要求1所述基于金属骨架材料的农药吸附可降解复合膜的制备方法,其特征在于,具体步骤如下:
配备喷雾原液:将载药MOF-5纳米颗粒按照质量分数10-15%,分散于甲醇中,利用超声分散,控制温度为20-25℃,分散时间为6-8h,获得喷雾原液;;
选用TYD01静电喷雾仪,调配TYD01静电喷雾仪工艺参数:喷雾条件控制在温度25℃-35℃,喷雾电压10-15kv,喷雾溶液流速为1-10ml,喷雾接收距离10-15cm,接收棍电极转速500-1000rpm,针头来回走速30-50cm/min,喷雾时间为24h-36h;
将可降解生物膜固定于TYD01静电喷雾仪载物电极板上,将载物电极板与正极线相连,按照上述操作参数对其进行喷雾;
将获得的载药后的可降解生物膜在自然条件下干燥,即得分布均匀的农药吸附可降解复合膜。
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ES2904323A1 (es) * | 2020-10-02 | 2022-04-04 | Univ Cadiz | Encapsulación de herbicidas para el control de malas hierbas |
WO2022069785A1 (es) * | 2020-10-02 | 2022-04-07 | Universidad De Cádiz | Encapsulación de herbicidas para el control de malas hierbas |
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