纳米SiO2–聚乙烯醇–γ聚谷氨酸复合膜材料制备及其性能研究  

Preparation and properties of nano-SiO2–polyvinyl alcohol–γ-polyglutamic acid composite film materials

作　　者：白杨 陈松岭[1] 范丽娟 杨明 邹洪涛[1] 张玉龙[1] BAI Yang;CHEN Song-ling;FAN Li-juan;YANG Ming;ZOU Hong-tao;ZHANG Yu-long(College of Land and Environment,Shenyang Agricultural University/Key Laboratory of Arable Land Conservation(Northeast China),Ministry of Agriculture/National Engineering Laboratory for Efficient Utilization of Soil and Fertilizer Resources,Shenyang 110866,China;Agriculture Service Station of Gaosheng Street,Panshan County,Panshan,Liaoning 124123,China)

机构地区：[1]沈阳农业大学土地与环境学院/农业部东北耕地保育重点实验室/土肥资源高效利用国家工程实验室,辽宁沈阳110866 [2]盘山县高升街道农业服务站,辽宁盘山124123

出　　处：《植物营养与肥料学报》2019年第12期2044-2052,共9页Journal of Plant Nutrition and Fertilizers

基　　金：国家自然科学基金项目(31572206);辽宁省重点研发计划项目(2019JH2/10200004);国家科技支撑项目(2015BAD23B0203);辽宁省“百千万人才工程”项目(2016921066);沈阳市中青年创新人才支持计划(RC1705580)

摘　　要：【目的】聚乙烯醇(polyvinyl alcohol,PVA)作为缓释肥包膜材料具有价格低廉、透性好、环保、少残留的优点,但耐水性能差,制成包膜肥料进入土壤后缓释效果不持久。γ聚谷氨酸(γ-PGA)是一种原料易得的肥料增效剂,利用纳米二氧化硅(nano-SiO2)和γ-PGA对聚合物PVA进行改性,并用改性后的PVA制备了缓释材料,优化nano-SiO2、γ-PGA和戊二醛的配比参数。【方法】试验采用三因素三水平L9(33)正交设计,三因素三水平是PVA浓度(因素A)4%、6%、8%,γ-PGA与PVA的质量配比(因素B)0.8∶3、1∶3、1.2∶3,戊二醛占PVA与γ-PGA体积之和比例(因素C)0.1%、0.2%、0.3%,以不添加戊二醛的9个处理做对照。用有机高分子聚合法制备复合膜,分析了不同原料配比制备的膜材料的吸水性和渗透性能,找出最优原料配比。在此基础上,在上述包膜材料中分别加入5、10和20 g/kg的nano-SiO2和少量无水乙醇制成复合膜,测定复合膜材料的吸水率、渗透率,分析了膜的红外光谱特征和表面微观结构变化,探讨其改性成膜机理。【结果】加入交联剂戊二醛后,复合膜材料的吸水率和渗透率均显著降低。当PVA浓度为4%,γ-PGA与PVA质量比为1.2∶3,戊二醛体积分数为0.3%时,复合膜材料的吸水率最低,为118%,铵离子和水的渗透率分别比对照降低了46.8%和23.0%。添加nano-SiO2后,各处理膜的吸水率均随nano-SiO2添加量的增加呈现先升高后降低的变化,当添加量为20 g/kg时,复合膜材料吸水率和NH4+渗透率最低,与不加nano-SiO2相比,复合膜材料吸水率和NH4+渗透率分别降低了6.8%~38.2%和23.8%~53.2%,而水渗透率增加了38.4%~67.7%。红外分析光谱结果表明,PVA和γ-PGA反应生成醚键;添加nano-SiO2处理的―OH伸缩振动峰变宽,透过率增加,并且出现了Si―O―Si摇摆振动和反对称伸缩振动;同时,从官能团特征看出复合膜中仍存在未反应的γ-PGA。扫描电镜结果显示纳米SiO^2-聚【Objectives】Polyvinyl alcohol(PVA),as a coating material of slow-released fertilizer,has advantages of low price,good permeability and friendly to environment.However,the water resistance of PVA film is poor.The slow-released effectiveness of fertilizer coated with the PVA does not last long in soil.γ-polyglutamic acid(γ-PGA)is a kind of environmental-friendly fertilizer synergist and easily obtained.In this study,we modified PVA properties by adding nano-SiO2,γ-PGA and glutaraldehyde,then prepared composite coating films using the modified PVA.The processing parameters were optimized.【Methods】The experiment adopted L9(33)orthogonal experimental design.The concentrations of PVA(factor A)were 4%(A1),6%(A2),8%(A3);the mass ratios ofγ-PGA to PVA(factor B)were 0.8∶3(B1),1∶3(B2),1.2∶3(B3);the volume fractions of glutaraldehyde inγ-PGA and PVA(factor C)were 0.1%(C1),0.2%(C2),0.3%(C3).Meanwhile,nine treatments without cross-linker were conducted as blank control.Organic high molecular polymerization method was used to prepare the composite materials,and the hydrophilism and permeability of composite materials were tested.Then composite films were prepared by adding 5,10 and 20 g/kg of nano-SiO2 and anhydrous ethanol.The hydrophilism,permeability,infrared spectrum characteristics and surface microstructure of composite materials were measured.【Results】The hydrophilism and permeability of the composite materials were significantly reduced after adding crosslinking agent.Under condition of factor A 4%,B 1.2∶3 and C 0.3%,the hydrophilism of composite materials was the lowest(118%),and the NH4+and water permeability were reduced by 46.8%and 23.0%,compared with the control.With increasing of nano-SiO2 addition,the hydrophilism of each treatment showed an up-and-down trend.When adding 20 g/kg of nano-SiO2,the hydrophilism and NH4+permeability of composite films were the lowest,which were decreased by 6.8%-38.2%and 23.8%-53.2%,respectively,compared with no nano-SiO2 treatment.However,the water permeabil

关 键 词：改性聚乙烯醇 γ聚谷氨酸 纳米二氧化硅 复合膜材料 红外光谱分析 

分 类 号：TQ449.1[化学工程—化学肥料工业]