CN103588561B - 光降解纳米聚合物包膜肥料及其制备方法 - Google Patents
光降解纳米聚合物包膜肥料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种光降解纳米聚合物包膜肥料及其制备方法。该包膜肥料,由肥料颗粒和包裹在所述肥料颗粒表面的包膜层组成;其中,构成所述包膜层的材料包括纳米光催化剂和聚烯烃树脂。所述的肥料颗粒为水溶性单质肥料或由所述水溶性单质肥料中的至少两种混合得到的复混肥;所述纳米光催化剂和聚烯烃树脂的质量比为0.1-6:100;所述的纳米光催化剂选自亲水性纳米二氧化钛和疏水性纳米二氧化钛中的至少一种。随着农业耕翻等田间作业,本发明提供的包膜肥料的残膜在光线的照射下或随时间的推移将进行有效的光降解,从而实现农业生产体系的循环发展。
Description
技术领域
本发明涉及一种光降解纳米聚合物包膜肥料及其制备方法,属于包膜肥料技术领域。
背景技术
包膜控释肥目前已成为缓控释肥领域的研发热点,其中聚烯烃树脂包膜肥因其优异的控释性能而成为市场上主流的控释肥产品,并得到了政府部门的大力推广。但是现行应用中仍存在一些问题亟待解决如残留包膜的降解,否则会造成所谓的“白色污染”等问题。
可降解塑料的出现为解决此类残膜的环境污染问题开辟了途径。现有的采用可降解聚烯烃塑料制备的包膜肥料主要有两大类:第一,生物降解型。主要是利用天然可降解材料如淀粉、琼脂、谷物粉和甲壳素等改性聚烯烃。为了保证包膜的控释性,可降解材料添加的量不足以影响聚烯烃的降解速率,因此通常情况下只有残膜中的可降解材料降解,聚烯烃仍然以一种低强度多孔形式的结构存在,其降解时间依然很长。另外,JP-A-7-33576公开了一种使用可生物降解聚已内酯树脂与低分子量聚烯烃树脂复合的聚烯烃包膜肥料,包衣膜具有一定的降解性能,然而膜的低机械性能导致其初期控释性能不足;第二,光降解型。US5009696公开了一种添加必需组分乙烯-一氧化碳共聚物的包膜肥料,包衣膜具有光降解性能,且最终能被微生物分解。该技术的不足是采用的包衣材料较难得到且成本较高。JP2002-234790和CN201010230156.0等采用添加光敏剂的方法制备了可降解聚烯烃包膜肥料。考虑到光敏剂降解塑料的降解率难以控制,产物可造成二次污染,且光敏剂易析出并迁移等问题,亟待开发一种廉价的新型可降解聚烯烃树脂包膜肥料以满足实际需要。
发明内容
本发明的目的在于针对现有技术中残余包膜累积的问题,利用超细纳米级粉体光催化原理,提供一种光降解纳米聚合物包膜肥料及其制备方法。
本发明提供的光降解纳米聚合物包膜肥料,由肥料颗粒和包裹在所述肥料颗粒表面的包膜层组成;其中,构成所述包膜层的材料包括纳米光催化剂和聚烯烃树脂。
上述包膜肥料中,构成所述包膜层的材料也可仅由所述纳米光催化剂和聚烯烃树脂组成。
所述肥料颗粒为水溶性单质肥料或由所述水溶性单质肥料中的至少两种混合得到的复混肥;
其中,所述水溶性单质肥料选自尿素、硫酸铵、氯化铵、硝酸铵、磷酸一铵、磷酸二铵、氯化钾、硫酸钾、硝酸钾、硫酸镁、硝酸镁、硫酸锌、硫酸铜或氯化锌;
所述纳米光催化剂为表面包有一层亲水层或疏水层的纳米二氧化钛;该纳米光催化剂中,二氧化钛表面包覆的亲水层或疏水层均可按常规方法制备而得;其中,表面包有一层亲水层的纳米二氧化钛亦称为亲水性二氧化钛;表面包有一层疏水层的纳米二氧化钛亦称为疏水性二氧化钛;
所述纳米光催化剂的粒径为20-200nm,具体为20、30、50、100、20-100、30-100、50-100、30-50或20-30nm,优选为20-50nm;
所述聚烯烃树脂具体选自聚乙烯、聚丙烯、聚苯乙烯和聚氯乙烯中的至少一种,具体选自粘均分子量为40700的低密度聚乙烯、粘均分子量为53870的聚苯乙烯、粘均分子量为81500的聚氯乙烯和粘均分子量为30886的由质量比为3:1的再生聚乙烯和10g再生聚丙烯组成的再生树脂中的至少一种;
所述纳米光催化剂和聚烯烃的质量比为0.1-6:100,具体为0.3-4:100,更具体为0.5-2.5:100、1.3:100、2.4:100或1.3-2.4:100。
构成所述包膜层的材料还含有填充材料;或者,
构成所述包膜层的材料由所述纳米光催化剂、聚烯烃树脂和填充材料组成。
所述填充材料选自滑石粉、聚烯烃填充母料、碳酸钙、膨润土、硅藻土、沸石分子筛、硫磺、硅灰石、石蜡、淀粉、纤维素、纤维素酯和乙烯-醋酸乙烯共聚物中的至少一种。
所述填充材料与聚烯烃树脂的质量比为0.5-7:10,具体为1-6:10,更具体为1.5-4.5:10、1.9:10、3.25:10或1.9-3.25:10。
本发明提供的制备上述包膜肥料的方法,包括如下步骤:将前述构成所述包膜层的材料按配比于有机溶剂中混匀得到包膜液,加热至100-110℃后,喷涂在所述肥料颗粒表面,干燥去除所述有机溶剂,得到所述包膜肥料;
上述方法中,所述有机溶剂为四氯乙烯;
构成所述包膜层的材料总重与有机溶剂的用量比为20-200g:1L,具体为40-150g:1L,更具体为45.6g:1L、53.6g:1L、54.6g:1L、45.6-53.6g:1L、45.6-54.6g:1L或53.6-54.6g:1L。
与现有技术相比,本发明的优点在于:由于纳米光降解剂在催化降解聚合物的过程中,不会产生二次污染且降解效率高,所以,随着农田耕翻等田间作业,暴露于光线下的残膜将进行有效的光降解,从而大幅减少残膜的累积量,实现农业生产体系的循环发展。
附图说明
图1为包膜肥料样品1和样品8在25℃水中的养分释放曲线图。
具体实施方式
下面结合具体实施例对本发明作进一步阐述,但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径而得。
实施例1、光降解纳米聚合物包膜肥料的制备
称取45g低密度聚乙烯(购于北京燕山石化股份有限公司,型号为1F7B,粘均分子量为40700)、8.5g填充材料滑石粉和0.6g粒径为50nm的纳米光催化剂表面包有一层疏水层的纳米二氧化钛(也即疏水性纳米二氧化钛,购于北京德科岛金科技有限公司),于1L四氯乙烯中在100-110℃混匀得到包膜液;将1kg尿素颗粒置于喷流塔中,干燥热风温度控制在100-110℃,在热空气的烘托下包膜液通过喷头喷涂到悬浮、流化的尿素颗粒表面上,溶剂挥发后制得包膜率为5%的包膜肥料,记为样品1。
实施例2:光降解纳米聚合物包膜肥料的制备
称取45g低密度聚乙烯(购于北京燕山石化股份有限公司,型号为1F7B,粘均分子量为40700)、4g淀粉、4.5g碳酸钙和0.6g粒径为20nm的纳米光催化剂表面包有一层疏水层的纳米二氧化钛(也即疏水性纳米二氧化钛,购于北京德科岛金科技有限公司),于1L四氯乙烯中在100-110℃混匀得到包膜液;将1kg尿素颗粒置于喷流塔中,干燥热风温度控制在100-110℃,在热空气的烘托下包膜液通过喷头喷涂到悬浮、流化的尿素颗粒表面上,溶剂挥发后制得包膜率为5%的包膜肥料,记为样品2。
实施例3:光降解纳米聚合物包膜肥料的制备
称取45g聚苯乙烯(购于中石化扬子巴斯夫,型号为EPS403W,粘均分子量为53870)、8.5g滑石粉和1.1g粒径为30nm的表面包有一层亲水层的纳米二氧化钛(也即亲水性纳米二氧化钛,购于德固赛公司,型号为P25),于1L四氯乙烯中在100-110℃混匀得到包膜液;将1kg尿素颗粒置于喷流塔中,干燥热风温度控制在100-110℃,在热空气的烘托下包膜液通过喷头喷涂到悬浮、流化的尿素颗粒表面上,溶剂挥发后制得包膜率为5%的包膜肥料,记为样品3。
实施例4:光降解纳米聚合物包膜肥料的制备
称取45g聚氯乙烯(购于江苏江东化工股份有限公司,型号为SG-3,粘均分子量为81500)和0.6g粒径为100nm的表面包有一层疏水层的纳米二氧化钛(也即疏水性纳米二氧化钛,购于北京德科岛金科技有限公司),于1L有机溶剂四氯乙烯中在100-110℃混匀得到包膜液;将1kg尿素颗粒置于喷流塔中,干燥热风温度控制在100-110℃,在热空气的烘托下包膜液通过喷头喷涂到悬浮、流化的尿素颗粒表面上,溶剂挥发后制得包膜率为5%的包膜肥料,记为样品4。
实施例5:光降解纳米聚合物包膜肥料的制备
称取40g再生树脂(由30g再生聚乙烯和10g再生聚丙烯组成,其粘均分子量为30886)、4g淀粉、9g聚烯烃填充母料(购于东莞市常新填充母料厂)和0.6g粒径为100nm的表面包有一层疏水层的纳米二氧化钛(也即疏水性纳米二氧化钛,购于北京德科岛金科技有限公司),于1L四氯乙烯中在100-110℃混匀得到包膜液;将1kg尿素颗粒置于喷流塔中,干燥热风温度控制在100-110℃,在热空气的烘托下包膜液通过喷头喷涂到悬浮、流化的尿素颗粒表面上,溶剂挥发后制得包膜率为5%的包膜肥料,记为样品5。
实施例6:光降解纳米聚合物包膜肥料的制备
将8.5g聚烯烃填充母料(购于东莞市常新填充母料厂)、0.6g粒径为100nm的表面包有一层疏水层的纳米二氧化钛(也即疏水性纳米二氧化钛,购于北京德科岛金科技有限公司)和45g低密度聚乙烯(购于北京燕山石化股份有限公司,型号为1F7B,粘均分子量为40700),于1L四氯乙烯中在100-110℃混匀得到包膜液;将1kg尿素颗粒置于喷流塔中,干燥热风温度控制在100-110℃,在热空气的烘托下包膜液通过喷头喷涂到悬浮、流化的尿素颗粒表面上,溶剂挥发后制得包膜率为5%的包膜肥料,记为样品6。
实施例7:光降解纳米聚合物包膜肥料的制备
称取45g低密度聚乙烯(购于北京燕山石化股份有限公司,型号为1F7B,粘均分子量为40700)、8.5g滑石粉和0.6g粒径为100nm的表面包有一层疏水层的纳米二氧化钛(也即疏水性纳米二氧化钛,购于北京德科岛金科技有限公司),于1L四氯乙烯中在100-110℃混匀得到包膜液;将1kg尿素颗粒置于喷流塔中,干燥热风温度控制在100-110℃,在热空气的烘托下将混匀的包膜液的80%通过喷头喷涂到悬浮、流化的尿素颗粒表面上,溶剂挥发后制得包膜率为5%的包膜肥料,记为样品7。
对照例1:聚合物包膜肥料的制备
与实施例1基本相同,不同之处为不含纳米光催化剂,记为样品8。
对照例2:含光敏剂光降解聚合物包膜肥料的制备
与实施例1基本相同,不同之处为将纳米光催化剂改为光敏剂硬脂酸铁,记为样品9。
包膜肥料养分控释性能的测定
采用水浸泡法测定包膜肥料样品1与对照实施例1制备的包膜肥料样品8的不同时间养分溶出量,结果如图1所示。
结果表明,添加纳米光催化剂后,包膜肥料养分释放期可延长半个多月。
包膜肥料残膜降解性能的测定
将包膜肥料释放后的残膜洗净置于自制的254nm紫外灯催化降解反应器内照射,样品距光源15cm,紫外灯强度为30W×2。光照一定时间后称重取样,计算残膜的失重率;
并分别采用乌氏粘度计和傅里叶红外光谱仪测定残膜粘均分子量和羰基指数。粘均分子量按GB1841-80聚烯烃树脂稀溶液粘度试验方法(聚丙烯和聚乙烯)和GB1632-79合成树脂常温稀溶液粘度测定方法(聚苯乙烯和聚氯乙烯)测定;红外光谱采用TENSOR27型傅立叶变换红外光谱仪(德国BROKER公司)进行表征。测量范围4000~500cm-1。
所得结果如表1所示。
表1、包膜肥料样品1-9的残膜降解性能
注:羰基指数为CI=A1715cm-1/A2020cm-1,A为峰的积分面积;
由表1可知,在光照条件下,添加光催化剂的残膜样品1-7的质量及粘均分子量呈明显下降趋势,羰基指数明显增加。
在其他原料配方相同的情况下,与添加光敏剂的对照样品9相比,样品1的失重率及粘均分子量降低率稍大,羰基指数达到7.5,而空白聚合物残膜对照样品8的变化不明显。以上结果得出,光催化剂可明显促进包膜肥料残膜的降解。
Claims (11)
1.一种包膜肥料,由肥料颗粒和包裹在所述肥料颗粒表面的包膜层组成;其特征在于:
构成所述包膜层的材料由所述纳米光催化剂和聚烯烃树脂组成;所述纳米光催化剂为表面包有一层亲水层或疏水层的纳米二氧化钛;
所述纳米光催化剂的粒径为20-100nm;
所述纳米光催化剂和聚烯烃的质量比为0.3-4:100;
所述聚烯烃树脂选自聚乙烯、聚丙烯、聚苯乙烯和聚氯乙烯中的至少一种。
2.根据权利要求1所述的肥料,其特征在于:所述肥料颗粒为水溶性单质肥料或由所述水溶性单质肥料中的至少两种混合得到的复混肥;
其中,所述水溶性单质肥料选自尿素、硫酸铵、氯化铵、硝酸铵、磷酸一铵、磷酸二铵、氯化钾、硫酸钾、硝酸钾、硫酸镁、硝酸镁、硫酸锌、硫酸铜和氯化锌中的至少一种;
所述纳米光催化剂的粒径为20-50nm。
3.根据权利要求1所述的肥料,其特征在于:所述纳米光催化剂和聚烯烃的质量比为0.5-2.5:100。
4.根据权利要求1-3任一所述的肥料,其特征在于:构成所述包膜层的材料还含有填充材料;
构成所述包膜层的材料由所述纳米光催化剂、聚烯烃树脂和填充材料组成。
5.根据权利要求4所述的肥料,其特征在于:所述填充材料选自滑石粉、聚烯烃填充母料、碳酸钙、膨润土、硅藻土、沸石分子筛、硫磺、硅灰石、石蜡、淀粉、纤维素、纤维素酯和乙烯-醋酸乙烯共聚物中的至少一种。
6.根据权利要求4所述的肥料,其特征在于:所述填充材料与聚烯烃树脂的质量比为0.5-7:10。
7.根据权利要求6所述的肥料,其特征在于:所述填充材料与聚烯烃树脂的质量比为1-6:10。
8.根据权利要求7所述的肥料,其特征在于:所述填充材料与聚烯烃树脂的质量比为1.5-4.5:10。
9.一种制备权利要求1-8任一所述肥料的方法,包括如下步骤:将权利要求1-8任一构成所述包膜层的材料按配比于有机溶剂中混匀得到包膜液,加热至100-110℃后,喷涂在所述肥料颗粒表面,干燥去除所述有机溶剂,得到所述包膜肥料。
10.根据权利要求9所述的方法,其特征在于:所述有机溶剂为四氯乙烯;
构成所述包膜层的材料总重与有机溶剂的用量比为20-200g:1L。
11.根据权利要求10所述的方法,其特征在于:构成所述包膜层的材料总重与有机溶剂的用量比为40-150g:1L。
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