CN116731489A - 一种降解型抗菌复合保鲜膜及其制备方法 - Google Patents
一种降解型抗菌复合保鲜膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种降解型抗菌复合保鲜膜,其包括PBAT、聚乳酸、甲基羟丙基纤维素醚、改性蒙脱土、滑石粉、助剂;其中,所述改性蒙脱土是蒙脱土接枝羧甲基壳聚糖的产物。该改性蒙脱土采用了功能性壳聚糖接枝改性后,使得蒙脱土本身和壳聚糖以共价键形式连接,而壳聚糖作为一种大分子聚合物,与PBAT和聚乳酸有优异的相容性,且易相互缠绕形成物理交联,从而使得蒙脱土能有效地分散于聚合物之中,而蒙脱土和滑石粉的极性也相近,从而极大地改善了整个组合物中的分散度和稳定性,使得组合物的可降解性更为稳定。
Description
技术领域
本发明属于塑料领域,具体涉及一种降解型抗菌复合保鲜膜及其制备方法。
背景技术
保鲜膜是一种塑料包装制品,通常以乙烯为母料通过聚合反应制成,保鲜膜可分为三大类:第一种是聚乙烯,简称PE;第二种是聚氯乙烯,简称PVC;第三种是聚偏二氯乙烯,简称PVDC。然而,上述塑料制品均是不能降解的产物,随着环保问题的日益突出,人们亟需逐步减少这些不可降解的塑料制品的使用量,寻找一种可降解的塑料制品刻不容缓。
而PBAT和乳酸类聚合物,是可生物降解塑料中的典型代表。PBAT属于热塑性可生物降解柔性材料,由对苯二甲酸丁二醇酯这一刚性链段,和己二酸丁二醇酯这一柔性链段组成。故其材料特性中,既具有脂肪族聚酯良好的生物可降解性能和柔韧性,又具有芳香族聚酯的良好力学性能、冲击性能和耐热性;并且由于其含有苯环结构,还使得材料兼具有良好的耐水性,因此是目前市场上商业化最为热门的可降解材料之一。聚乳酸(PLA)是一种新型的生物降解材料,使用可再生的植物资源(如玉米)所提出的淀粉原料制成。淀粉原料经由糖化得到葡萄糖,再由葡萄糖及一定的菌种发酵制成高纯度的乳酸,再通过化学合成方法合成一定分子量的聚乳酸。其具有良好的生物可降解性,使用后能被自然界中微生物完全降解,最终生成二氧化碳和水,不污染环境,这对保护环境非常有利,是公认的环境友好材料。普通塑料的处理方法依然是焚烧火化,造成大量温室气体排入空气中,而聚乳酸塑料则是掩埋在土壤里降解,产生的二氧化碳直接进入土壤有机质或被植物吸收,不会排入空气中,不会造成温室效应。
然而,在以PBAT和乳酸类聚合物为基材的塑料制品中,还会存在一些无机类的颗粒物质,用来增加塑料制品的力学性能或刚性,其在共混熔融成型的过程中,很难体现与聚合物的相容性,比如聚乳酸是一种生物型材料,其与无机填料颗粒相容性很差。在成型后,容易造成力学性能不稳定,可降解性不均匀的不理想情况。特别是可降解塑料或保鲜膜一般适用于户外场合,极端气候会加剧这一现象。
因此,亟需找到一种方法,来克服上述基于PBAT和乳酸类聚合物的保鲜膜的缺陷。
发明内容
为了克服目前技术中所存在的缺点和不足,本发明公开了一种基于PBAT的降解型保鲜膜,其与聚乳酸进行共混作为基材,并且添加了改性蒙脱土,该改性蒙脱土采用了功能性壳聚糖接枝改性后,使得蒙脱土本身和壳聚糖以共价键形式连接,而壳聚糖作为一种大分子聚合物,与PBAT和聚乳酸有优异的相容性,且易相互缠绕形成物理交联,从而使得蒙脱土能有效地分散于聚合物之中,而蒙脱土和滑石粉的极性也相近,从而极大地改善了整个组合物中的分散度和稳定性,使得组合物的可降解性更为稳定。
本发明的一个目的,在于提供一种降解型抗菌复合保鲜膜。
所述降解型抗菌复合保鲜膜的成分包括PBAT、聚乳酸、甲基羟丙基纤维素醚、改性蒙脱土、滑石粉、助剂;
其中,所述改性蒙脱土是蒙脱土接枝羧甲基壳聚糖的产物。
进一步地,所述助剂包括润滑剂、抗氧化剂、扩链剂、抗菌剂的一种或多种。
进一步地,所述降解型抗菌复合保鲜膜包括质量份数如下的成分:
PBAT 20-30份
聚乳酸 20-30份
甲基羟丙基纤维素醚 5-8份
改性蒙脱土 4-6份
滑石粉 4-6份
助剂。
进一步地,所述羧甲基壳聚糖选自O-羧甲基壳聚糖、N-羧甲基壳聚糖、N,O-羧甲基壳聚糖的一种或多种。
本发明的另一个目的在于提供上述降解型抗菌复合保鲜膜的制备方法,其包括如下步骤:
S1. 改性蒙脱土的制备:将羟基化的蒙脱土、羧甲基壳聚糖与水共混,然后加热超声,得到所述改性蒙脱土;
S2. 将所述改性蒙脱土与其他成分进行物理共混,并通过挤出机进行熔融,然后挤出成型。
进一步地,所述羟基化的蒙脱土与所述羧甲基壳聚糖的质量比为1:50-100。
进一步地,所述加热的温度为80-90℃。
进一步地,所述熔融的温度为160-180℃。
进一步地,所述加热的时间为1-3 h。
本发明具有以下有益效果:
PBAT和乳酸类聚合物本身具有优异的可降解性能,但是与其他无机颗粒或助剂复配后,如何保证优异且稳定的组合物的可降解性能,是亟需考虑的问题。本发明以接枝了壳聚糖的改性蒙脱土作为桥梁,增加了有机聚合物和无机小分子颗粒之间的相容性。壳聚糖本身就是一种大分子聚合物,生物性能优异,与PBAT和聚乳酸有优异的相容性,且易相互缠绕形成物理交联,从而使得蒙脱土能有效地分散于聚合物之中;而蒙脱土作为无机小分子物质,与其他助剂极性相近,从而极大地改善了整个组合物中的分散度和稳定性,使得组合物的可降解性更为稳定。
具体实施方式
为了更清楚地说明本发明的技术方案,列举如下实施例。实施例中所出现的原料、反应和后处理手段,除非特别声明,均为市面上常见原料,以及本领域技术人员所熟知的技术手段。
本发明实施例中所述的PBAT,采购自巴斯夫(中国)有限公司,规格为EcoflexC1200;
本发明实施例中所述的聚乳酸,采购自美国NatureWorks公司,型号为4032D;
本发明的助剂包括润滑剂硬酯酸锌、抗氧化剂对苯二酚、扩链剂ADR-4370、抗菌剂苯并异噻唑啉酮;四者质量比为1:2:1:1;
本发明羧甲基壳聚糖为O-羧甲基壳聚糖;
蒙脱土和滑石粉的平均粒径为100 nm。
本发明实施例中,改性蒙脱土的制备方法为:将蒙脱土浸泡在浓硫酸和双氧水的混合液(7:3,v/v)中10 h,然后过滤,清水洗涤,然后干燥,得到羟基化的蒙脱土;
然后将羟基化蒙脱土和羧甲基壳聚糖共混(1:50,m/m),然后加入纯水,稍微加热搅拌,使得羧甲基壳聚糖完全溶于水中;
然后在80℃下超声,反应1 h,然后过滤掉溶液,分别用乙醇和清水洗涤一次,得到改性蒙脱土。
实施例1
一种降解型抗菌复合保鲜膜,其包括如下质量份数的成分:
PBAT 20份
聚乳酸 20份
甲基羟丙基纤维素醚 5份
改性蒙脱土 4份
滑石粉 4份
助剂 2份。
上述降解型抗菌复合保鲜膜的制备方法为:
将上述各个成分,按质量份数,投入双螺杆挤出机中加热熔融,设置各个工段的加工温度为160-170℃,使得基料熔融,并与其他成分共混均匀。经熔融挤出后,通过风机吹制膜泡,等膜泡大小稳定后,调节吹胀比为3.0,使得薄膜宽幅达到1 m;通过调节主机转速和牵引速率,调节薄膜厚度为12 μm。所得薄膜双向剖开,收卷放置。得到产物。
实施例2
一种降解型抗菌复合保鲜膜,其包括如下质量份数的成分:
PBAT 30份
聚乳酸 30份
甲基羟丙基纤维素醚 8份
改性蒙脱土 6份
滑石粉 6份
助剂 3份。
上述降解型抗菌复合保鲜膜的制备方法为:
将上述各个成分,按质量份数,投入双螺杆挤出机中加热熔融,设置各个工段的加工温度为165-175℃,使得基料熔融,并与其他成分共混均匀。经熔融挤出后,通过风机吹制膜泡,等膜泡大小稳定后,调节吹胀比为3.0,使得薄膜宽幅达到1 m;通过调节主机转速和牵引速率,调节薄膜厚度为15 μm。所得薄膜双向剖开,收卷放置。得到产物。
实施例3
一种降解型抗菌复合保鲜膜,其包括如下质量份数的成分:
PBAT 25份
聚乳酸 25份
甲基羟丙基纤维素醚 6份
改性蒙脱土 5份
滑石粉 5份
助剂 3份。
上述降解型抗菌复合保鲜膜的制备方法为:
将上述各个成分,按质量份数,投入双螺杆挤出机中加热熔融,设置各个工段的加工温度为170-180℃,使得基料熔融,并与其他成分共混均匀。经熔融挤出后,通过风机吹制膜泡,等膜泡大小稳定后,调节吹胀比为3.0,使得薄膜宽幅达到1 m;通过调节主机转速和牵引速率,调节薄膜厚度为20 μm。所得薄膜双向剖开,收卷放置。得到产物。
对比例1
对比例1中的复合保鲜膜,所用成分、成分质量份数和制备方法与实施例1均相同,唯一不同在于,对比例1中的改性蒙脱土,用等质量份数的蒙脱土代替。
对比例2
对比例2中的复合保鲜膜,所用成分、成分质量份数和制备方法与实施例1均相同,唯一不同在于,对比例2中的改性蒙脱土,是用蒙脱土与月桂酸偶联所得,即改性蒙脱土是经月桂酸接枝所得产物。
测试例1
将上述实施例1、对比例1-2所得的复合保鲜膜进行力学性能测试。测试方法按照ASTM D638-02塑料拉伸性能测试标准进行。
具体地,将上述新鲜制得的样品,进行力学性能测试并记载数据;然后将上述样品,放置在室外露天环境下60天(日平均气温为30℃),然后再进行力学性能测试并记载数据。
所得结果如表1所示。
表1 实施例1、对比例1-2所得的基于PBAT的可降解塑料地膜的力学性能测试
从表1中可以看出,新制得的不同样品的弹性模量数值相当,均在23-24 MPa左右,这也是较为常见的塑料所具有的弹性模量范围;而当在室外露天放置60天后,由于室外天气气温较高且日晒雨淋,导致保鲜膜的发脆和发硬趋势较为明显,即发生了老化行为。然而,实施例1的样品相比于对比例1-2,其老化趋势较弱,这可能是因为改性蒙脱土作为有机和无机成分的桥梁作用,一方面具有大量的壳聚糖支化链可以与其他聚合物相容性良好,另一方面壳聚糖本身所具有大量羟基,又可以和无机颗粒表面所自带的羟基发生氢键作用;并且蒙脱土本身和其他无机颗粒极性相似,从而使得改性蒙脱土的体系较为分散和稳定,不易在极端气候下发生相分离等现象,维持了保鲜膜的力学性能。
测试例2
将上述新制得的实施例1和对比例1-2所得的基于PBAT的可降解塑料地膜,进行生物降解性能测试。所采用的的测试方法根据自然掩埋法进行,将上述样品埋于公司研发部前的试验地中,掩埋深度为10-20 cm,并且保证掩埋测试阶段完全避光,掩埋时间为200天。经过200天后,将保鲜膜挖掘出来,视觉查看降解结果。所得结果如表2所示。
表2 样品60天后的降解率
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (9)
1.一种降解型抗菌复合保鲜膜,其特征在于,所述降解型抗菌复合保鲜膜的成分包括PBAT、聚乳酸、甲基羟丙基纤维素醚、改性蒙脱土、滑石粉、助剂;
其中,所述改性蒙脱土是蒙脱土接枝羧甲基壳聚糖的产物。
2.根据权利要求1所述降解型抗菌复合保鲜膜,其特征在于,所述助剂包括润滑剂、抗氧化剂、扩链剂、抗菌剂的一种或多种。
3.根据权利要求1所述降解型抗菌复合保鲜膜,其特征在于,所述降解型抗菌复合保鲜膜包括质量份数如下的成分:
PBAT 20-30份
聚乳酸 20-30份
甲基羟丙基纤维素醚 5-8份
改性蒙脱土 4-6份
滑石粉 4-6份
助剂。
4.根据权利要求1所述降解型抗菌复合保鲜膜,其特征在于,所述羧甲基壳聚糖选自O-羧甲基壳聚糖、N-羧甲基壳聚糖、N,O-羧甲基壳聚糖的一种或多种。
5.权利要求1-4任一项所述降解型抗菌复合保鲜膜的制备方法,其特征在于,包括如下步骤:
S1. 改性蒙脱土的制备:将羟基化的蒙脱土、羧甲基壳聚糖与水共混,然后加热超声,得到所述改性蒙脱土;
S2. 将所述改性蒙脱土与其他成分进行物理共混,并通过挤出机进行熔融,然后挤出成型。
6.根据权利要求5所述降解型抗菌复合保鲜膜的制备方法,其特征在于,所述羟基化的蒙脱土与所述羧甲基壳聚糖的质量比为1:50-100。
7.根据权利要求5所述降解型抗菌复合保鲜膜的制备方法,其特征在于,所述加热的温度为80-90℃。
8.根据权利要求5所述降解型抗菌复合保鲜膜的制备方法,其特征在于,所述熔融的温度为160-180℃。
9.根据权利要求5所述降解型抗菌复合保鲜膜的制备方法,其特征在于,所述加热的时间为1-3 h。
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