CN113462069A - 一种高强度抗撕裂的农用大棚膜 - Google Patents
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Abstract
本案涉及一种高强度抗撕裂的农用大棚膜，是由可降解聚酯、纳米粉体、茂金属线性聚乙烯、线性低密度聚乙烯、无滴剂和填料制成。本发明通过对聚乙烯膜配方的改进，以线性低密度聚乙烯作为大棚膜基础树脂，在配方中添加茂金属聚乙烯以提高膜的力学性能和光学性能，同时通过通过含氟硅的可降解聚酯，极大的提高了普通聚乙烯膜的抗撕裂强度；聚酯材料降解性能好，添加至聚乙烯膜中对环境不会造成影响；纳米粉体以及其它助剂进一步提升膜的长期无滴消雾效果和耐候保温性。
Description
技术领域
本发明涉及塑料膜领域，具体为一种高强度抗撕裂的农用大棚膜。
背景技术
农用大棚膜是现代农业中常用的生产工具，是我国塑料工业中的重要组成部分。将农用大棚膜搭配竹结构或钢结构的框架形成一个温室空间，不仅能促进作物生长、早熟、增长，同时也使得人们可以吃到反季节蔬菜。农用塑料主要以聚氯乙烯(PVC)和聚乙烯(PE)为原料，PVC棚膜应用于上个世纪60年代，然而PVC膜不能燃烧处理，易产生有毒气体逐渐被市场淘汰；PE膜透光性好且无毒，但耐候性和保温性较差，使用寿命短。茂金属聚乙烯分子结构规整，相对分子质量分布窄、支链少，因而力学强度和光学性能表现较为优异，是新一代的线型低密度聚乙烯，目前已被应用于农用大棚膜上。然而，较窄的茂金属聚乙烯的加工性能较差，在吹塑时常出现膜泡不稳定、熔体破裂等情况，挤出造粒时也更加困难。
聚酯塑料是一种新型高分子薄膜材料，相较于PVC膜和PE膜具有更高的透光性，以及更高的机械强度和耐腐蚀性能。但是聚酯大棚膜要大范围推广使用还需要解决一些疑难问题，例如由于大棚膜长期暴露于自然环境中，因此要提高其耐老化性；此外，虽然聚酯大棚膜具有较高的机械强度，但若薄膜产生缺口，则薄膜很容易从这个缺口处撕裂，使用寿命大大降低。
发明内容
针对现有技术中的不足之处，本发明在线性低密度聚乙烯中结合茂金属聚乙烯和聚酯以及其它填充材料和助剂等得到的混合物，在制备过程中加工性能好，制得的大棚膜同时具备高强度和抗撕裂性。
为实现上述目的，本发明提供如下技术方案：
一种高强度抗撕裂的农用大棚膜，是由可降解聚酯、纳米粉体、茂金属线性聚乙烯、线性低密度聚乙烯、无滴剂和填料制成；其中，所述可降解聚酯的结构式如下：
m＞n＞10。
进一步地，所述纳米粉体选自纳米SiO2、纳米CaCO3、纳米TiO2中的一种或多种。
进一步地，所述无滴剂选自单油酸甘油酯、单硬脂酸山梨醇酐酯、单月桂酸山梨醇酐酯、聚氧乙烯山梨醇酐单月桂酸酯、硬脂酸二聚甘油酯中的任意两种组合物。
进一步地，所述填料由30％抗氧化剂、20％聚乙烯蜡和50％滑石粉组成。
进一步地，各原料成分按重量配比计为：可降解聚酯20～40％、纳米粉体5～10％、茂金属线性聚乙烯20～40％、线性低密度聚乙烯50～70％、无滴剂1～2％和填料5～10％。
与现有技术相比，本发明的有益效果是：本发明通过对聚乙烯膜配方的改进，以线性低密度聚乙烯作为大棚膜基础树脂，在配方中添加茂金属聚乙烯以提高膜的力学性能和光学性能，同时通过含氟硅的可降解聚酯，极大的提高了普通聚乙烯膜的抗撕裂强度；聚酯材料降解性能好，添加至聚乙烯膜中对环境不会造成影响；纳米粉体以及其它助剂进一步提升膜的长期无滴消雾效果和耐候保温性。
具体实施方式
下面将结合实施例对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
一种高强度抗撕裂的农用大棚膜，其原料包括可降解聚酯20～40％、纳米粉体5～10％、茂金属线性聚乙烯20～40％、线性低密度聚乙烯50～70％、无滴剂1～2％和填料5～10％；其中，
所述可降解聚酯由MPDL
和氟硅乙烯基单体
共聚制成，所述MPDL可依据文献Chem.Rev.2017,117,1319-1406合成；所述氟硅乙烯基单体的反应方程式如下：
在反应瓶中加入三乙氧基乙烯基硅烷和对甲苯磺酸(PTSA)，加入四氢呋喃搅拌混匀，加热回流，滴加含3,3,3-三氟-1-丙醇的四氢呋喃溶液，滴加完毕后保温反应1h，过滤，减压蒸馏制得氟硅单体。
在氮气氛围下，将氟硅乙烯基单体和MPDL按照2:8的摩尔比添加到反应瓶中，加入引发剂AIBN和溶剂四氢呋喃，在60℃下搅拌反应24h，聚合物在无水乙醚中沉淀，真空干燥即得。通过GPC检测分子量Mn＝10400g/mol，PDI＝1.56，通过核磁检测m/n比值3/1。由于MPDL的反应活性较低，通过提高反应体系中的MPDL投料量来提高聚合物中聚酯结构的含量，同时使聚合物倾向于无规共聚物，从而使聚合物主链降解更加彻底。
此外，引入的聚酯结构可以使后续制备的大棚膜具备更高的透光性能，而通过与氟硅乙烯基单体的共聚也使得大棚膜具备更高的拉伸强度，抗撕裂能力得以提升。氟硅乙烯基单体以硅原子为中心，氟原子以三氟甲基形式连接于单体末端，在迁移的过程中伸向棚膜的内侧，加快水蒸气转化为流滴铺展于棚膜表面，从而起到消雾的作用。
无机纳米粉体选自纳米SiO2、纳米CaCO3、纳米TiO2中的一种或多种。
线性低密度聚乙烯是制备大棚膜的基础树脂，通过添加茂金属线性聚乙烯提高大棚膜的机械强度，再配合上述可降解聚酯以及其它材料使得大棚膜具备抗撕裂性能，优异的耐候性和保温性，同时透光性较好。
所述填料由30％抗氧化剂、20％聚乙烯蜡和50％滑石粉组成；其中抗氧化剂为常用添加剂，可优选为酚类抗氧剂。
可降解聚酯20～40％、纳米粉体5～10％、茂金属线性聚乙烯20～40％、线性低密度聚乙烯50～70％、无滴剂1～2％和填料5～10％。
实施例1：
可降解聚酯30％、纳米粉体(纳米CaCO3、纳米TiO2)5％、茂金属线性聚乙烯20％、线性低密度聚乙烯50％、无滴剂(单油酸甘油酯、单硬脂酸山梨醇酐酯)1％和填料6％。
实施例2：
可降解聚酯40％、纳米粉体(纳米CaCO3、纳米SiO2)6％、茂金属线性聚乙烯25％、线性低密度聚乙烯70％、无滴剂(聚氧乙烯山梨醇酐单月桂酸酯、硬脂酸二聚甘油酯中)1％和填料8％。
对比例1：
可降解聚酯制备工艺同上，其中，将单体MPDL替换成BMDO(同样参考文献Chem.Rev.2017,117,1319-1406合成)，其余条件不变。
组合物其余成分及含量同实施例1。
对比例2：
可降解聚酯制备工艺同上，其中，在氟硅乙烯基单体的制备过程中将3,3,3-三氟-1-丙醇替换成四氟丙醇，其余条件不变。
组合物其余成分及含量同实施例1。
对比例3：
可降解聚酯0％、纳米粉体(纳米CaCO3、纳米TiO2)5％、茂金属线性聚乙烯20％、线性低密度聚乙烯50％、无滴剂(单油酸甘油酯、单硬脂酸山梨醇酐酯)1％和填料6％。
按照上述实施例1-2以及对比例1-3的配方挤出吹塑制得大棚膜，对大棚膜的性能进行测试。
力学性能：拉伸强度、断裂伸长率和直角撕裂强度在室温下进行，测试过程拉力为1000N，拉伸速度为50mm/min。样品裁剪成哑铃型，拉伸性能测试过程按照GB/T1040.3-2006进行。直角撕裂样品裁剪尺寸为100mm×20mm，按照GB/T 529-2008进行，每组样品测量5次，取平均值。
透光率通过光电雾度计测试，对5个不同部位进行测试取平均值，测试结果记录在表1中。
表1
薄膜的力学性能主要取决于基体树脂的力学性能，因此仅仅依靠添加助剂难以满足薄膜实际应用需求，本案通过在聚乙烯基体树脂中添加茂金属聚乙烯有效提高薄膜强度，再通过聚酯树脂可有效提高薄膜的撕裂强度；且透光率提升也较为明显，聚酯降解性能好，可以减少环境污染。对比例1和对比例2在可降解聚酯制备的单体选择上有所区别，以BMDO替换MPDL，苯环位置或氟位置的改变造成聚合物链中空间位阻增大或氢键能力减弱，拉伸强度和抗撕裂能力有所下降；对比例3在不使用可降解聚酯的情况下制得的大棚膜各项性能均较差。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。
Claims (5)
1.一种高强度抗撕裂的农用大棚膜，其特征在于，是由可降解聚酯、纳米粉体、茂金属线性聚乙烯、线性低密度聚乙烯、无滴剂和填料制成；其中，所述可降解聚酯的结构式如下：
m＞n＞10。
2.如权利要求1所述的高强度抗撕裂的农用大棚膜，其特征在于，所述纳米粉体选自纳米SiO2、纳米CaCO3、纳米TiO2中的一种或多种。
3.如权利要求1所述的高强度抗撕裂的农用大棚膜，其特征在于，所述无滴剂选自单油酸甘油酯、单硬脂酸山梨醇酐酯、单月桂酸山梨醇酐酯、聚氧乙烯山梨醇酐单月桂酸酯、硬脂酸二聚甘油酯中的任意两种组合物。
4.如权利要求1所述的高强度抗撕裂的农用大棚膜，其特征在于，所述填料由30％抗氧化剂、20％聚乙烯蜡和50％滑石粉组成。
5.如权利要求1所述的高强度抗撕裂的农用大棚膜，其特征在于，各原料成分按重量配比计为：可降解聚酯20～40％、纳米粉体5～10％、茂金属线性聚乙烯20～40％、线性低密度聚乙烯50～70％、无滴剂1～2％和填料5～10％。
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