CN107474494B - 一种可机械覆膜的超薄耐候全生物降解地膜及其制备方法 - Google Patents

一种可机械覆膜的超薄耐候全生物降解地膜及其制备方法 Download PDF

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CN107474494B
CN107474494B CN201710572615.5A CN201710572615A CN107474494B CN 107474494 B CN107474494 B CN 107474494B CN 201710572615 A CN201710572615 A CN 201710572615A CN 107474494 B CN107474494 B CN 107474494B
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米庆华
徐静
张坤
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Shandong Agricultural University
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Abstract

本发明是属于生物降解高分子材料领域，尤其涉及一种可机械覆膜的超薄耐候全生物降解地膜及其制备方法，该地膜以全生物降解树脂、增强增韧增透助剂、易加工助剂和稳定性助剂组成，其中增强增韧增透助剂的加入解决了超薄地膜机械强度差、易断裂，难以机械覆膜的难题；易加工助剂解决了超薄地膜加工难开口、加工效率低的难题；稳定性助剂解决了生物降解地膜耐候性差的问题；并通过优选全生物降解树脂的种类，结合功能性助剂开发出厚度4‑6μm、降解周期2‑6个月可调的超薄超透明超强全生物可控降解地膜，地膜透明性高，透光率＞90％，雾度＜13％；机械强度高，拉伸强度＞25MPa，满足普通覆膜机对地膜强度要求。

Description

一种可机械覆膜的超薄耐候全生物降解地膜及其制备方法
技术领域
本发明属于农业材料领域，具体涉及一种可机械覆膜的超薄耐候全生物降解地膜及其制备方法。
背景技术
地膜在农业生产中，起到巨大作用，然而目前所采用的塑料地膜绝大多数为难以短时期降解的聚烯烃类地膜或者添加了淀粉和光降解剂的不完全降解聚烯烃类地膜。这些地膜材料的使用，造成环境的“白色污染”，为人类可持续发展带来了安全隐患。全生物降解地膜是由完全生物降解塑料通过吹塑或者流延加工而成，能被微生物完全分解，其降解的最终产物为二氧化碳和水，可完全为自然界消纳，因此以全生物降解地膜代替目前的聚烯烃类产品，是解决农田白色污染的重要手段，有着重要的开发利用前景。
目前德国巴斯夫、日本三菱、法国利马格兰集团以及国内的广东金发、山东意可曼、杭州鑫富药业等都有该类地膜的生产，并在在玉米、棉花、花生、烟草、大蒜、马铃薯、草莓等作物上进行了试验。但是普遍存在地膜厚度高，成本居高不下；减薄后加工稳定性差，难开口；力学性能差，无法机械覆膜；耐候性差，强光照下易变脆，降解周期过快等问题，严重制约了全生物降解地膜的推广和应用。
发明内容
本发明针对现有技术存在的诸多不足之处，提供了一种可机械覆膜的超薄耐候全生物降解地膜及其制备方法，该地膜以全生物降解树脂、增强增韧增透助剂、易加工助剂和稳定性助剂组成，其中增强增韧增透助剂的加入解决了超薄地膜机械强度差、易断裂，难以机械覆膜的难题；易加工助剂解决了超薄地膜加工难开口、加工效率低的难题；稳定性助剂解决了生物降解地膜耐候性差的问题；并通过优选全生物降解树脂的种类，结合功能性助剂开发出厚度4-6μm、降解周期2-6个月可调的超薄超透明超强全生物可控降解地膜，地膜透明性高，透光率＞90％，雾度＜13％；机械强度高，拉伸强度＞25MPa，满足普通覆膜机对地膜强度要求。拉伸强度、断裂伸长率、直角撕裂强度均符合PE地膜机械铺膜标准，物理机械性能优于或符合GB 13735-92规定。
本发明的具体技术方案是：
一种可机械覆膜的超薄耐候全生物降解地膜，其主要组分按重量份计为：
全生物降解树脂70-90份、增强增韧增透助剂1-8份、易加工助剂1-3份，稳定性助剂1-2份；
其中所述的全生物降解树脂为聚己二酸/对苯二甲酸丁二酯，以及聚乳酸、聚碳酸亚丙酯的一种或几种；
其中，聚己二酸/对苯二甲酸丁二酯作为主要组分，配合聚乳酸、聚碳酸亚丙酯的一种或两种，其中聚己二酸/对苯二甲酸丁二酯占全生物降解树脂的85-95％。
所述的聚己二酸/对苯二甲酸丁二酯熔体流动速率为1-2g/10min，羟值小于15；其中所述的聚乳酸熔体流动速率为2-5g/10min，羟值小于15；其中所述的聚碳酸亚丙酯熔体流动速率为1-2g/10min，羟值小于15。
所述的增强增韧增透剂为无机增强增韧增透剂、有机增强增韧增透剂的一种或几种：所述的无机增强增韧增透剂，主要选自疏水型纳米二氧化硅，其中所述的疏水型纳米二氧化硅尺寸为2-5nm；所述的有机增强增韧增透剂，为阿克玛AX-8900或ADX-1200s树脂相容剂。
所述的易加工助剂为聚合物微球PMMA，二氧化硅微球中的一种或两种；所述的聚合物微球尺寸为1-5μm，所述的二氧化硅微球尺寸为1-5μm；
所述的稳定性助剂紫外光稳定剂、紫外光吸收剂的一种或两种，
更进一步的，所述的紫外线吸收剂为低挥发性苯并三唑类紫外吸收剂Tinuvin234，所述的紫外线稳定剂为空间位阻胺类稳定剂5050H。
本发明中，发明人将聚己二酸/对苯二甲酸丁二酯作为主要的全生物降解树脂，控制其熔体流动速率为1-2g/10min，羟值小于15；主要利用了其良好的韧性，配合其他树脂实现了性能互补，使其具有较好的成膜性和加工性。
本发明的另外一个特点就是提供了所述可机械覆膜的超薄耐候全生物降解地膜的制备方法，包括以下步骤：
(1)将全生物降解树脂、增强增韧增透助剂、稳定性助剂、易加工助剂按重量份配比高速混合机搅拌5-8min混匀后投入双螺杆挤出机中，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；
(2)将全生物降解地膜专用吹膜料投入吹膜机进行吹膜，得到膜厚为4-6μm的超薄地膜，其中，吹胀比为1.5-3.0，模口间隙为0.8-1.8。
上述参数中进一步限制了模口间隙和吹胀比，从而确保地膜的性能更佳。
与现有技术相比，本发明的优点在于：
1.该地膜厚度仅为4-6μm，减薄后的地膜降低了全生物降解地膜的单位面积成本。
2.该地膜采用增强增韧增透助剂，不仅力学性能得到改善(拉伸强度高于25MPa，满足机械覆膜标准要求)，透光率也明显提高(透光率＞90％，雾度＜13％)。
3.该地膜采用微球型加工型助剂，使吹膜加工稳定，膜片开口顺滑易加工。
4.该地膜采用全生物降解树脂与功能性助剂复配，结合不同厚度，提高地膜耐候性，地膜降解周期2-6个月可控且可以完全降解，完全没有任何污染。
具体实施方式
实施例1
一种可机械覆膜的超薄耐候全生物降解地膜，其原料组成按照重量份计为：
按照下述步骤制备而成：
步骤1将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；
步骤3将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为3.0，模口间隙为1.0。厚度为0.004mm，幅宽2000mm。
实施例2
一种可机械覆膜的超薄耐候全生物降解地膜，其原料组成按照重量份计为：
按照下述步骤制备而成：
步骤1将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；
步骤3将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为2.5，模口间隙为1.0。厚度为0.006mm，幅宽900mm。
实施例3
一种可机械覆膜的超薄耐候全生物降解地膜，其原料组成按照重量份计为：
按照下述步骤制备而成：
步骤1将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜吹膜料；
步骤3将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为2.5，模口间隙为0.8。厚度为0.005mm，幅宽900mm。
实验例
按照GB 13735-92塑料拉伸性能的测定，拉伸速率200mm/min。所得可机械覆膜的超薄耐候全生物降解地膜各性能如表1所示。
应用实例1 应用实例2 应用实例3
厚度(μm) 4 6 5
透光率(％) 91.5 90.8 91.2
雾度 11.7 12.1 12
拉伸强度(MPa) 26 33 30
断裂伸长率(％) 450 672 560
直角撕裂强度(MPa) 99 110 107
吹塑膜泡开口性 开口顺滑，不断膜 开口顺滑，不断膜 开口顺滑，不断膜
通过超薄超强超透明全生物降解地膜降解性验证试验：可知本发明所制备的厚度4-6μm可机械覆膜的超薄耐候全生物降解地膜，地膜透明性高，透光率＞90％，雾度＜13％；机械强度高，拉伸强度＞25MPa，可以使用普通覆膜机进行机铺。越冬大蒜覆膜栽培可以满足大蒜6个月生长期需求，地膜可以完全降解。

Claims (2)

1.一种可机械覆膜的超薄耐候全生物降解地膜，其原料组成按照重量份计为：
聚己二酸/对苯二甲酸丁二酯 88.7份
聚乳酸 5份
疏水型纳米二氧化硅 2份
二氧化硅微球 3份
紫外线吸收剂Tinuvin 234 1.5份
按照下述步骤制备而成：
步骤1将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜专用吹膜料；
步骤3将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为3.0，模口间隙为1.0， 厚度为0.004mm，幅宽2000mm；
其中所述的疏水型纳米二氧化硅粒径为2-5nm，二氧化硅微球的粒径为1μm。
2.一种可机械覆膜的超薄耐候全生物降解地膜，其原料组成按照重量份计为：
聚己二酸/对苯二甲酸丁二酯 84.2份
聚乳酸 5份
聚亚丙基碳酸酯 5份
疏水型纳米二氧化硅 2份
二氧化硅微球 3份
紫外线稳定剂Uvinul® 5050H 0.5份
紫外线吸收剂Tinuvin 234 0.5份
按照下述步骤制备而成：
步骤1将上述组分置于高速搅拌机进行搅拌混合，无需加温，高速混合机搅拌5-8min；
步骤2将步骤1混合好的物料经双螺杆造粒机，于135-160℃挤出、风冷造粒，得到全生物降解地膜吹膜料；
步骤3将步骤2吹膜料在吹膜机上进行吹膜，吹胀比为2.5，模口间隙为0.8， 厚度为0.005mm，幅宽900mm；
其中所述的疏水型纳米二氧化硅粒径为2-5nm，二氧化硅微球的粒径为2-3μm。
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