CN112159544B - 环保型高阻隔薄膜及其制备方法 - Google Patents
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Abstract
一种环保型高阻隔薄膜及其制备方法,该环保型高阻隔薄膜包括阻隔层和分别位于所述阻隔层两侧的两个基层,所述阻隔层和所述基层通过多层共挤工艺形成的复合结构,其中所述基层包括如下重量份配比的原料:己二酸丁二醇酯‑对苯二甲酸丁二醇酯共聚物60~80份、增塑剂0~5份、聚丙烯酸酯0~25份、聚碳酸亚丙酯0~20份和聚己内酯/聚乙烯吡咯烷酮共混物0.2~5份;所述阻隔层包括如下重量份配比的原料:聚碳酸亚丙酯70~90份、纳米介孔材料1~10份、分散剂0.2~1份。本发明中的环保型高阻隔薄膜具有良好的阻隔性能和降解性能。
Description
技术领域
本发明涉及高分子材料技术领域,特别是涉及一种环保型高阻隔薄膜及其制备方法。
背景技术
各类产品的包装均需要应用到包装材料,包装材料已成为生活和生产中必不可少的一部分。现有的包装材料大多以聚乙烯、聚氯乙烯等材料制成,其降解能力差,带来了严重的环境污染问题。随着环境和资源问题的重视度提高,研发和生产可生物降解包装材料成为当前重要的进程。
PBAT(聚已二酸/对苯二甲酸丁二酯)是最具商业开发价值的生物可降解塑料,其由己二酸丁二醇酯(PBA)和对苯二甲酸醇酯(PBT)组成的共聚物。PBAT具有优越的物理特性和降解性,但普通的PBAT存在着阻隔性能差和降解速度太慢等缺陷,影响了其在市场上的接受度。
发明内容
鉴于上述状况,有必要针对现有技术中PBAT材料的薄膜降解能力差和阻隔性能不理想的问题,提供一种环保型高阻隔薄膜及其制备方法。
一种环保型高阻隔薄膜,包括阻隔层和分别位于所述阻隔层两侧的两个基层,所述阻隔层和所述基层通过多层共挤工艺形成的复合结构,其中
所述基层包括如下重量份配比的原料:己二酸丁二醇酯-对苯二甲酸丁二醇酯共聚物60~80份、增塑剂0~5份、聚丙烯酸酯0~25份、聚碳酸亚丙酯0~20份和聚己内酯/聚乙烯吡咯烷酮共混物0.2~5份;
所述阻隔层包括如下重量份配比的原料:
聚碳酸亚丙酯70~90份、纳米介孔材料1~10份、分散剂0.2~1份。
该环保型高阻隔薄膜为通过多层共挤工艺形成的复合层架构,其至少包括三层,即位于中间的阻隔层和分别位于该阻隔层两侧的两个基层。形成该基层的原料包括如下组分:己二酸丁二醇酯-对苯二甲酸丁二醇酯共聚物(PBAT)、增塑剂、聚丙烯酸酯、聚碳酸亚丙酯和聚己内酯/聚乙烯吡咯烷酮共混物。
其中,PBAT为基层材料中的主要组分,其己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物,兼具PBA和PBT的特性,既有较好的延展性和断裂伸长率,也有较好的耐热性和冲击性能;此外,还具有优良的生物降解性。
增塑剂、聚丙烯酸酯和聚碳酸亚丙酯可根据材料需要可选择性的加入。在基层的材料中增加适量增塑剂时可以改善薄膜的拉伸性能;增加适量的聚碳酸亚丙酯可增强薄膜的柔韧性、弹性以及耐候性;增加适量的聚碳酸亚丙酯可提高薄膜的气体阻隔性,使薄膜对氧气、二氧化碳以及水蒸气具有良好的阻隔能力。
聚己内酯/聚乙烯吡咯烷酮共混物为聚己内酯(PCL)和聚乙烯吡咯烷酮(PVP)的共混物,其可以被细菌或真菌迅速降解,在薄膜材料中增加该共混物可以进一步提高该薄膜的降解速率,并且通过对聚己内酯和聚乙烯吡咯烷酮的成分的控制可以使其共混物具有不同的降解速率,从而影响最终成型薄膜的降解性能。
该阻隔层起到对气体阻隔的主导作用,其主要由聚碳酸亚丙酯70~90份、纳米介孔材料1~10份和分散剂0.2~1份组成。该聚碳酸亚丙酯具有良好的气体阻隔性能,且在该阻隔层的原料中添加纳米介孔材料可以增强该阻隔层的阻隔性。纳米介孔材料为含有介孔尺度的多孔材料,例如纳米介孔二氧化硅,其孔径一般介于2纳米~100纳米,其具有极高的比表面积和规则有序的孔道结构使聚碳酸亚丙酯形成致密的阻隔层。
进一步的,上述环保型高阻隔薄膜,其中,所述聚己内酯/聚乙烯吡咯烷酮共混物中聚己内酯与聚乙烯吡咯烷酮的质量比为1.5~5:1。
进一步的,上述环保型高阻隔薄膜,其中,所述增塑剂为邻苯二甲酸酯、磷酸三苯酯、柠檬酸三正丁酯和环氧大豆油中的至少一种。
进一步的,上述环保型高阻隔薄膜,其中,所述基层的原料中还含有抗粘连剂。
进一步的,上述环保型高阻隔薄膜,其中,所述抗粘连剂为石蜡或碳酸钙。
通过在基层中加入适量的抗粘连剂有利于产品脱模,提高薄膜良率。
进一步的,上述环保型高阻隔薄膜,其中,所述分散剂为烷基酚聚氧乙烯醚甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚甲醛缩合物磷酸盐、亚甲基二萘磺酸钠、烷基萘磺酸盐、EO-PO嵌段聚醚、苯乙烯苯酚聚氧乙烯醚磷酸中的任意一种或多种的组合。
进一步的,上述环保型高阻隔薄膜,其中,所述环保型高阻隔薄膜的厚度可为20~350um,且所述阻隔层的厚度为所述基层厚度的1.5~5倍。
本发明实施例还提供了一种环保型高阻隔薄膜的制备方法,包括:
分别将第一基层、阻隔层和第二基层的原料按照既定重量份配比混合均匀,并分别加入对应的双螺杆挤出机中熔融塑化;
将熔融塑化后的第一基层、阻隔层和第二基层的原料从对应的双螺杆挤出机中挤出至150~230℃的模头中汇流形成三层复合结构,再经过冷却辊在20~70℃温度下冷却,形成三层共挤出结构的膜片;
将所述膜片在40~90℃预热后进行纵向拉伸,并在20~90℃温度下热定型,再进行横向拉伸,并在50~160℃温度下热定型;
将拉伸后的膜片进行电晕或火焰处理后收卷。
本发明中的环保型高阻隔薄膜具有三层结构,包括中间的阻隔层和两侧的基层。其中基层结构中通过添加聚己内酯/聚乙烯吡咯烷酮共混物来调节薄膜的生物降解速率,使该薄膜达到理想的降解速率;阻隔层包括聚碳酸亚丙酯和纳米介孔材料,纳米介孔材料在分散剂的作用均匀分散在阻隔层中聚碳酸亚丙酯,在纳米介孔材料的多孔通道的作用下,聚碳酸亚丙酯与纳米介孔材料形成致密排列的阻隔结构,极大的提高了该薄膜的阻隔性能。
具体实施方式
为使本发明的目的、特征和优点能够更加明显易懂,下面结合实施例对本发明的具体实施方式做详细的说明。实施例中给出了本发明的若干实施例。但是,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施例。相反地,提供这些实施例的目的是使对本发明的公开内容更加透彻全面。
实施例1
一种环保型高阻隔薄膜,包括阻隔层和分别位于阻隔层两侧的两个基层,阻隔层和基层通过多层共挤工艺形成的复合结构,该基层包括如下重量份配比的原料:己二酸丁二醇酯-对苯二甲酸丁二醇酯共聚物70份和聚己内酯/聚乙烯吡咯烷酮共混物2份;该阻隔层包括如下重量份配比的原料:聚碳酸亚丙酯80份、纳米介孔材料5份、EO-PO嵌段聚醚0.5份。
其中,该聚己内酯/聚乙烯吡咯烷酮共混物中聚己内酯与聚乙烯吡咯烷酮的质量比为5:1。通过在基层的原料中增加聚己内酯/聚乙烯吡咯烷酮共混物可以在一定程度上增加该基层的降解性能。
该阻隔层主要成分采用气阻隔性能良好的聚碳酸亚丙酯,其在纳米介孔材料的作用下形成致密的排列结构,极大的提高了该阻隔层的阻隔性能。
EO-PO嵌段聚醚作为阻隔层材料中的分散剂,EO-PO嵌段聚醚为聚醚与聚氧乙烷(EO)和聚氧丙烷(PO)组成,通常是EO与PO无规共聚而成嵌段聚醚,EO为亲水基是EO,PO为疏水基,EO-PO嵌段聚醚具有良好的分散性,使该纳米介孔材料在聚碳酸亚丙酯分子间充分分散。
该环保型高阻隔薄膜的制备方法包括以下步骤:
按照配比准备两个基层的原料,并分别将两个基层的原料混合均匀后分别加入到对应的双螺杆挤出机中熔融塑化,其中,熔融塑化的温度为180摄氏度;
按照配比准备阻隔层的原料,并将该阻隔层的原料混合均匀后在双螺杆挤出机中熔融塑化,其熔融塑化的温度为200℃;
将两个基层熔融塑化后的原料以及阻隔层熔融塑化后的原料分别从对应的双螺杆挤出机中挤出至200℃的模头中汇流形成三层复合结构,再经过冷却辊在30℃温度下冷却,形成三层共挤出结构的膜片;
将所述膜片在50℃预热后进行纵向拉伸,拉伸倍数3,并在50℃温度下热定型,再进行横向拉伸,拉伸倍数为5,并在100℃温度下热定型;
将拉伸后的膜片进行电晕或火焰处理后收卷,得到该环保型高阻隔薄膜。
该环保型高阻隔薄膜的厚度可控制在20~350um,阻隔层的厚度大于基层的厚度,一般来说阻隔层的厚度为基层厚度的1.5~5倍,以保障薄膜的气体阻隔性。如本实施例中,其厚度为200um,阻隔层的厚度为120um,两个基层的厚度均为40um。
实施例2
本实施例与实施例1基本相同,不同之处在于:
该阻隔层中聚碳酸亚丙酯90份、纳米介孔材料10份、EO-PO嵌段聚醚1份。
实施例3
本实施例与实施例1基本相同,不同之处在于:
该分散剂选用亚甲基二萘磺酸钠和烷基萘磺酸盐的混合物。
实施例4
本实施例与实施例1基本相同,不同之处在于:
该聚己内酯/聚乙烯吡咯烷酮共混物5份。
实施例5
本实施例与实施例4基本相同,不同之处在于:
该聚己内酯/聚乙烯吡咯烷酮共混物中聚己内酯与聚乙烯吡咯烷酮的质量比为2:1
实施例6
本实施例与实施例1基本相同,不同之处在于:
该基层的原料中还添加有增塑剂2份、聚丙烯酸酯15份和聚碳酸亚丙酯10份,其中增塑剂为磷酸三苯酯。
实施例7
本实施例与实施例6基本相同,不同之处在于:
该增塑剂为环氧大豆油。
对照例1
本实施例与实施例1基本相同,不同之处在于:
该环保型高阻隔薄膜不含有阻隔层。
对照例2
本实施例与实施例1基本相同,不同之处在于:
阻隔层的原料中未添加纳米介孔材料。
对照例3
本实施例与实施例1基本相同,不同之处在于:
该基层的原料中不添加聚己内酯/聚乙烯吡咯烷酮共混物。
将以上实施例和对照例所得的环保型高阻隔薄膜进行生物降解性能测试、气体阻隔性能测试和拉伸性能测试。
该生物降解性能测试模拟一般土壤中的环境条件,并通过质量损失发来测定各个实施例中的薄膜的生物降解性能。测试结果如表1所示,通过上述实施例1至8可知,通过增加聚己内酯/聚乙烯吡咯烷酮共混物使该薄膜具有良好的生物降解性能,在测试时间为120天的时候薄膜降解率均在90%以上。
表1
并且,通过实施例1、实施例4实施例5和对照例3可知,聚己内酯/聚乙烯吡咯烷酮共混物的生物降解性能具有良好的促进作用。尤其是在第40天至第80天这一时间段内,薄膜中添加聚己内酯/聚乙烯吡咯烷酮共混物后降解速率急剧增加。
该气体阻隔性能测试主要测量薄膜对氧气、二氧化碳和水蒸气的阻隔性能。如表2所示,通过实施例1至实施例7可知,本申请中的制备得到的薄膜其对氧气、二氧化碳以及水蒸气均有良好的阻隔性能,其中,氧气的透过率在22cm3/(m2·24h·atm)以下,二氧化碳的透过率在252cm3/(m2·24h·atm)以下,水蒸气的透过率在18cm3/(m2·24h·atm)以下。
并且,通过实施例1和2以及对照例2可知,通过在薄膜材料中增加纳米介孔材料可以显著改善薄膜的生物降解性能。纳米介孔材料在分散剂的作用均匀分散在阻隔层中聚碳酸亚丙酯,在纳米介孔材料的多孔通道的作用下,聚碳酸亚丙酯与纳米介孔材料形成致密排列的阻隔结构,极大的提高了该薄膜的阻隔性能。
表2
进一步的,如表3所示,通过拉伸性能测试对该薄膜进行纵向方向上的拉伸,可知,实施例1至实施例7中的环保型高阻隔薄膜均具有良好的拉伸性能,特别是在加入适量的增塑剂、聚丙烯酸酯和聚碳酸亚丙酯后,拉伸性能有显著的改善。不同的增塑剂对薄膜材料拉伸性能的影响不同,本发明实施例中磷酸三苯酯对薄膜材料拉伸性能的改善效果优于其他增塑剂。
除此之外,从表2中还可得知,在基层原料中添加增塑剂份、聚丙烯酸酯份和聚碳酸亚丙酯份后,薄膜的阻隔性能也有所改善,尤其在增塑剂为磷酸三苯酯时,薄膜的阻隔性能显著提高,这是由于磷酸三苯酯能显著提高各组分之间的融合程度,提高各组分的聚集程度。
表3
拉伸强度Mpa | 断裂伸长率% | |
实施例1 | 52 | 421 |
实施例2 | 49 | 431 |
实施例3 | 51 | 425 |
实施例4 | 51 | 426 |
实施例5 | 52 | 419 |
实施例6 | 28 | 580 |
实施例7 | 38 | 530 |
对照例1 | 41 | 512 |
对照例2 | 48 | 441 |
对照例3 | 51 | 425 |
在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (6)
1.一种环保型高阻隔薄膜,其特征在于,包括阻隔层和分别位于所述阻隔层两侧的两个基层,所述阻隔层和所述基层通过多层共挤工艺形成的复合结构,其中
所述基层包括如下重量份配比的原料:己二酸丁二醇酯-对苯二甲酸丁二醇酯共聚物60~80份、增塑剂0~5份、聚丙烯酸酯0~25份、聚碳酸亚丙酯0~20份和聚己内酯/聚乙烯吡咯烷酮共混物0.2~5份;
所述阻隔层包括如下重量份配比的原料:
聚碳酸亚丙酯70~90份、纳米介孔材料1~10份、分散剂0.2~1份;
所述分散剂为烷基酚聚氧乙烯醚甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚甲醛缩合物磷酸盐、亚甲基二萘磺酸钠、烷基萘磺酸盐、EO-PO嵌段聚醚、苯乙烯苯酚聚氧乙烯醚磷酸中的任意一种或多种的组合;
所述聚己内酯/聚乙烯吡咯烷酮共混物中聚己内酯与聚乙烯吡咯烷酮的质量比为1.5~5:1。
2.如权利要求1所述的环保型高阻隔薄膜,其特征在于,所述增塑剂为邻苯二甲酸酯、磷酸三苯酯、柠檬酸三正丁酯和环氧大豆油中的至少一种。
3.如权利要求1所述的环保型高阻隔薄膜,其特征在于,所述基层的原料中还含有抗粘连剂。
4.如权利要求3所述的环保型高阻隔薄膜,其特征在于,所述抗粘连剂为石蜡或碳酸钙。
5.如权利要求1所述的环保型高阻隔薄膜,其特征在于,所述环保型高阻隔薄膜的厚度为20~350um,且所述阻隔层的厚度为所述基层厚度的1.5~5倍。
6.一种如权利要求1至5任意一项所述的环保型高阻隔薄膜的制备方法,其特征在于,包括:
分别将第一基层、阻隔层和第二基层的原料按照既定重量份配比混合均匀,并分别加入对应的双螺杆挤出机中熔融塑化;
将熔融塑化后的第一基层、阻隔层和第二基层的原料从对应的双螺杆挤出机中挤出至150~230℃的模头中汇流形成三层复合结构,再经过冷却辊在20~70℃温度下冷却,形成三层共挤出结构的膜片;
将所述膜片在40~90℃预热后进行纵向拉伸,并在20~90℃温度下热定型,再进行横向拉伸,并在50~160℃温度下热定型;
将拉伸后的膜片进行电晕或火焰处理后收卷。
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