CN107903597A - 抑制杂草的全生物降解地膜及其制备方法 - Google Patents

抑制杂草的全生物降解地膜及其制备方法 Download PDF

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CN107903597A
CN107903597A CN201711254381.6A CN201711254381A CN107903597A CN 107903597 A CN107903597 A CN 107903597A CN 201711254381 A CN201711254381 A CN 201711254381A CN 107903597 A CN107903597 A CN 107903597A
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付宇经
宣兆志
阎宝林
李开磊
张鑫科
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Shandong Tianye Biodegradation New Material Technology Co Ltd
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Abstract

一种抑制杂草的全生物降解地膜，以重量份数计，由以下组分制成：聚乳酸60‑80份，聚己二酸对苯二甲酸丁二酯10‑30份，炭黑母料5‑10份，抗氧剂0.1‑1份，柔性改性剂10‑20份；其中，炭黑母料以重量份数计，由以下组分制成：PBAT 30‑80份，炭黑15‑35份，除草剂5‑25份，炭黑分散处理剂1‑10份。该地膜利用炭黑的吸附功能，将除草剂混合到炭黑中，通过高速搅拌混合，然后在生物降解树脂载体作用下，造粒制作成炭黑母料，然后按比例添加到降解地膜料中吹塑薄膜；由于混合处理过程中除草剂进入到炭黑内部空隙中，由炭黑包裹，因而在吹制地膜过程中以及存放地膜过程中除草剂不析出。

Description

抑制杂草的全生物降解地膜及其制备方法
技术领域
本发明涉及一种抑制杂草的全生物降解地膜及其制备方法，主要用于覆盖地膜，能够有效抑制杂草的生长，属于高分子材料加工与应用领域。
背景技术
随着塑料行业的发展，塑料产品用途越来越广泛，其中作为农作物覆盖用的农用塑料地膜因具有保温、保湿等作用被广泛应用；但石油基树脂的不可降解性给土壤环境造成较大污染，因而目前已有不少降解地膜来替代非降解地膜；覆盖地膜在有利于农作物生长的同时，杂草滋生也较为严重，因而需要人工除草或者打除草剂，劳动力成本较高；除草剂地膜是近年来发展起来的新的化学除草方法，在降低劳动力成本，减少农药对人身体的毒害以及环境污染方面起到了一定效果。
目前应用的除草剂地膜，有的采用喷涂、涂抹等方式制成膜，有的将除草剂共混在原料中改性、造粒，但涂抹除草剂会浪费大量人力物力；也有不少这方面的专利，如申请号为201210525950.7的专利，一种可以完全生物降解的除草地膜，是由PBAT、PBAT+PLA或PBAT+PPC和除草剂、扩链剂、脱模剂组成，利用搅拌机将PBAT、PBAT+PPC或PBAT+PLA和除草剂、扩链剂、脱模剂搅拌均匀后，用双螺杆挤出机对共混后的材料进行挤出改性、造粒；申请号为95108803.3的专利，一种可控光和生物双降解除草农用地膜，其组份包含聚乙烯树脂50—70份,改性淀粉30—50份、光敏剂0.02—0.30份,促氧化剂0.01—0.08份、降解控制剂0.02—0.30份、除草剂0.08—0.2份。该膜添加了除草剂,使可降解地膜在降解过程中,具备了控制杂草丛生的作用；申请号201510563522.7的专利，一种农作物可控降解杀虫灭草全生物降解地膜，由以下组份组成，聚烃基烷酸脂70-79%，聚乳酸8-25%，纳米钙粉1-4%，氯虫苯甲酰胺0.05-0.25%，百草枯0.05-0.25%，多菌灵0.1-0.5%，以及生物降解剂，混合，高速捏合，然后吹膜成型；申请号为201610985359.8的专利，一种生物降解除草地膜在马铃薯栽培中的应用，由以下组分组成，生物降解树脂70-97%，生物降解除草剂母粒3-30%，该母料由10-60%除草剂和0.5-7%的山梨醇月桂酸酯和丙二醇脂肪酸酯组成，且经过超声处理，但并不能阻止除草剂析出损失。综合分析以上专利发现，除草剂都是直接添加到塑料中或者做成除草剂母料再添加到塑料中挤出吹膜。众所周知，除草剂与共混的塑料相容性如果极佳，那么除草剂在塑料中不会析出，就起不到除草目的；除草剂与共混的塑料必须不相容，在雨水和太阳光暴晒过程中除草剂析出才能达到除草效果；但是，与塑料不相容的除草剂加到塑料中极易析出，往往杂草还没生长，除草剂已经析出完毕或者所剩无几，甚至在地膜储存运输过程中已经大量析出，使得地膜中除草剂浓度大幅降低，起不到除草效果。
发明内容
为解决上述问题，本发明专利利用炭黑的吸附功能，将除草剂混合到炭黑中，通过高速搅拌混合，然后在生物降解树脂载体作用下，造粒制作成炭黑母料，然后按比例添加到降解地膜料中吹塑薄膜；由于混合处理过程中除草剂进入到炭黑内部空隙中，由炭黑包裹，因而在吹制地膜时以及地膜存放过程中除草剂不析出。
该降解地膜是将除草剂混合在炭黑中，利用炭黑的吸附作用，将除草剂充分吸附在炭黑内部空隙中，在生物降解树脂载体作用下，通过造粒制作成炭黑母料，然后添加到生物降解树脂中吹塑黑白相间地膜；这种地膜优势是在储存和运输过程中，除草剂由于炭黑内部空隙的吸附包覆不会出现流失，但在地膜使用过程中，在光和热的作用下，除草剂就会慢慢析出，随地膜表面上由于地表水蒸发而成的水珠流到土地表面，从而起到除草作用；特别是随着中午太阳强光直射，除草剂析出就会越多，对杂草的杀灭有着极好的效果，且该地膜具有生物降解功能，在堆肥条件下能够完全生物降解成二氧化碳和水，不会对土壤和环境造成污染。
本发明技术方案如下：一种抑制杂草的全生物降解地膜，该地膜由以下组分配比共混组成（重量份数）：聚乳酸（PLA），60-80份，聚己二酸对苯二甲酸丁二酯（PBAT），10-30份，炭黑母料5-10份，抗氧剂0.1-1份，柔性改性剂10-20份。
所述炭黑母料以重量份数计，由以下组分制成： PBAT30-80份；炭黑15-35份；除草剂5-25份；炭黑分散处理剂1-10份。
所述聚己二酸对苯二甲酸丁二酯（PBAT）为生物降解聚酯，分子量10000-30000。
所述聚乳酸（PLA）分子量8-15万。该树脂在堆肥条件下，180天相对生物分解率超过90%。
其中抗氧剂优选2，6-二叔丁基-4-甲基苯酚和2，4，6-三[2-（2羟基-3-叔丁基-5-甲基苯基）-4-甲基-6-叔丁基酚基]-氰尿酸酯复配，重量比为1：（0.5-1）。
所述柔性改性剂为聚己内酯，平均分子量为1000-3000，柔软性极佳，作为PLA树脂的增韧剂。
所述炭黑为卡博特生产的牌号为M717炭黑，该炭黑具有良好的黑度、易分散，具有吸附性好的特性。
所述除草剂为4,6-双(异丙氨基)-2-甲硫基-1,3,5-三嗪或2-甲基-4-氯苯氧乙酸。
所述炭黑分散处理剂为复合型单烷氧基脂肪酸钛酸酯，牌号为NDZ-131。
本发明一种抑制杂草的全生物降解地膜制备方法为：
（1）除草剂溶液配制：用丙酮或者乙醇溶剂与除草剂按1-1.5：1比例混合搅拌，将除草剂配置成丙酮或乙醇溶液；
（2）母料的制备：将炭黑，除草剂溶液，炭黑分散处理剂按比例称好，一同放入高速混合机中混合处理，并升温至50-70℃，以保证丙酮或乙醇充分挥发；高速混合机采用无级变速混合，快慢结合，慢速搅拌450-600转/分钟，高速搅拌转速为1200-1500转/分钟，混合时间5-10分钟，然后，再按比例加入聚己二酸对苯二甲酸丁二酯，继续混合2-5分钟，放出混合物料；
（3）将PLA、PBAT、柔性改性剂、抗氧剂以及混合好的炭黑母料按比例称好，放入高速搅拌机中混合5min，放出物料；
（4）将混合好的物料在双螺杆挤出机中挤出造粒，挤出造粒温度110～170℃，经塑料切粒机切成粒料；
(5)将造好的粒料在吹膜机上在170-195℃条件下吹膜薄膜，膜厚为大于8μm，得到本发明抑制杂草的全生物降解地膜。
本发明有益效果如下：该降解地膜是将除草剂混合在炭黑中，利用炭黑的吸附作用，将除草剂充分吸附在炭黑内部空隙中，在生物降解树脂载体作用下，通过造粒制作成炭黑母料，然后添加到生物降解树脂中吹塑黑白相间地膜。
这种地膜优势是在储存和运输过程中，除草剂由于炭黑内部空隙的吸附包覆不会出现流失，但在地膜使用过程中，在光和热的作用下，除草剂就会慢慢析出，随地膜表面上由于地表水蒸发而成的水珠流到土地表面，从而起到除草作用；特别是随着中午太阳强光直射，除草剂析出就会越多，对杂草的杀灭有着极好的效果，且该地膜能够完全生物降解成二氧化碳和水，不会对土壤和环境造成污染。本发明所用材料易得，选择的生产工艺技术简单成熟，具有实用性和可操作性。
具体实施方式
下面结合实施例，对本发明作进一步的说明，但并不因此限制本发明。
实施例中PLA聚乳酸的牌号为牌号Revode110，浙江海正生物材料有限公司，密度1.25±0.05g/cm3，熔点140-155℃；
PBAT的牌号和指标如下：牌号TH801T,东莞仁聚生物全降解塑胶有限公司，熔点110-120℃，密度1.2-1.28g/cm3；所述炭黑为卡博特生产的牌号为M717炭黑，所述除草剂为4,6-双(异丙氨基)-2-甲硫基-1,3,5-三嗪；炭黑分散处理剂为复合型单烷氧基脂肪酸钛酸酯，牌号为NDZ-131。
炭黑母料组成为：聚己二酸对苯二甲酸丁二酯（PBAT）:65%；炭黑：20%；除草剂：10%；炭黑分散处理剂：5%。
抗氧剂为2，6-二叔丁基-4-甲基苯酚和2，4，6-三[2-（2羟基-3-叔丁基-5-甲基苯基）-4-甲基-6-叔丁基酚基]-氰尿酸酯复配，重量比为1：1。
下表为实施例和比较例。实施例和比较例的区别在于，比较例1在实施例6的基础上去掉了聚己内酯；比较例2采用的炭黑母料没有添加炭黑分散处理剂。
表1 本发明的实施例和比较例配方，kg
。
表2实施例和比较例的性能测试结果
。
实施例和比较例地膜的制备方法如下：
（1）除草剂溶液配制：用丙酮或者乙醇溶剂与除草剂按1.2：1比例混合搅拌，将除草剂配置成丙酮溶液；
（2）母料的制备：将炭黑，除草剂溶液，炭黑分散处理剂按比例称好，一同放入高速混合机中混合处理，并升温至60℃，以保证丙酮或乙醇充分挥发；高速混合机采用无级变速混合，快慢结合，慢速搅拌450-600转/分钟，高速搅拌转速为1200-1500转/分钟，混合时间6分钟，然后，再按比例加入聚己二酸对苯二甲酸丁二酯，继续混合5分钟，放出混合物料；
（3）将PLA、PBAT、柔性改性剂、抗氧剂以及混合好的炭黑母料按比例称好，放入高速搅拌机中混合5min，放出物料；
（4）将混合好的物料在双螺杆挤出机中挤出造粒，挤出造粒温度110～170℃，经塑料切粒机切成粒料；
(5)将造好的粒料在吹膜机上在170-195℃条件下吹膜薄膜，膜厚为8μm，得到本发明抑制杂草的全生物降解地膜。
实施例和比较例地膜在一定条件下析出性能测试结果如表3。
表3 降解PVC组合物实施例、比较例的性能测试结果
。
测试条件：将一定重量的地膜样品放入3%洗涤剂浓度的溶液中，在室温下浸渍168小时，然后取出在室温下放置干燥48小时，称重计算地膜重量损失，用百分数表示，数值越低说明越不易析出，反之则析出越严重。
经种植花生测试，本发明的地膜中农药为缓释，药效时间长，同样种植条件下，实施例6的花生产量比对比例1高10%；比对比例2高17%。
由性能测试结果可以看出，本发明生物降解地膜吹塑的地膜抗析出除草剂能力均优于比较例。

Claims (9)

1.一种抑制杂草的全生物降解地膜，以重量份数计，由以下组分制成：聚乳酸60-80份，聚己二酸对苯二甲酸丁二酯10-30份，炭黑母料5-10份，抗氧剂0.1-1份，柔性改性剂10-20份。
2.根据权利要求1所述抑制杂草的全生物降解地膜，其特征在于所述炭黑母料以重量份数计，由以下组分制成：聚己二酸对苯二甲酸丁二酯30-80份，炭黑15-35份，除草剂5-25份，炭黑分散处理剂1-10份。
3.根据权利要求1所述抑制杂草的全生物降解地膜，其特征在于所述聚己二酸对苯二甲酸丁二酯分子量10000-30000。
4.根据权利要求1所述抑制杂草的全生物降解地膜，其特征在于所述聚乳酸分子量8-15万。
5.根据权利要求1所述抑制杂草的全生物降解地膜，其特征在于所述柔性改性剂为聚己内酯，平均分子量为1000-3000。
6.根据权利要求2所述抑制杂草的全生物降解地膜，其特征在于所述炭黑为卡博特M717炭黑。
7.根据权利要求2所述抑制杂草的全生物降解地膜，其特征在于所述除草剂为4,6-双(异丙氨基)-2-甲硫基-1,3,5-三嗪或2-甲基-4-氯苯氧乙酸。
8.根据权利要求2所述抑制杂草的全生物降解地膜，其特征在于所述炭黑分散处理剂为复合型单烷氧基脂肪酸钛酸酯，牌号为NDZ-131。
9.根据权利要求2所述抑制杂草的全生物降解地膜的制备方法，其特征在于依次包括如下步骤：
（1）除草剂溶液配制：用丙酮或者乙醇溶剂与除草剂按1-1.5：1比例混合搅拌，将除草剂配置成丙酮或乙醇溶液；
（2）将炭黑，除草剂溶液，炭黑分散处理剂按比例称好，一同放入高速混合机中混合处理，并升温至50-70℃，以保证丙酮或乙醇充分挥发；高速混合机采用无级变速混合，快慢结合，慢速搅拌450-600转/分钟，高速搅拌转速为1200-1500转/分钟，混合时间5-10分钟，然后，再按比例加入聚己二酸对苯二甲酸丁二酯，继续混合2-5分钟，放出混合物料；
（3）将PLA、PBAT、柔性改性剂、抗氧剂以及混合好的炭黑母料按比例称好，放入高速搅拌机中混合5min，放出物料；
（4）将混合好的物料在双螺杆挤出机中挤出造粒，挤出造粒温度110～170℃，经塑料切粒机切成粒料；
（5）将造好的粒料在吹膜机上在170-195℃条件下吹膜薄膜，膜厚为大于8μm，得到抑制杂草的全生物降解地膜。
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