CN114055877A - 耐热、低水蒸气透过率且可生物降解的纸塑复合材料及其制备方法和应用 - Google Patents
耐热、低水蒸气透过率且可生物降解的纸塑复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种耐热、低水蒸气透过率且可生物降解的纸塑复合材料及其制备方法和应用,该纸塑复合材料以纸张为基材,以多层可降解薄膜为阻隔层;多层可降解薄膜为PBS和改性PBAT形成的多层共挤膜,改性PBAT中含有片状填料;先将片状填料与PBAT树脂熔融共混挤出造粒,后采用与PBS多层共挤吹塑的方法制备多层共挤膜,再将多层共挤膜通过水性复膜胶与纸张复合,得到纸塑复合材料;PBS膜可以提高薄膜整体的耐热性,而且纸塑包装还可以做到热压封合。与现有技术相比,本发明薄膜与纸张复合后能够达到PE、PP等纸塑复合包装的阻水蒸气性能,可完全生物降解,环保性能好,能够防止对环境的污染,可应用于食品、医药制品等领域。
Description
技术领域
本发明涉及包装材料技术领域,尤其是涉及一种耐热、低水蒸气透过率且可生物降解的纸塑复合材料及其制备方法和应用。
背景技术
PBAT、PBS是可降解生物基聚合物,在自然界中可生物降解生成二氧化碳和水,对环境友好。具有完全生物可降解性能,较好的物理机械性能和加工性能,适用于加工注塑制品,发泡材料、薄膜、纤维等,主要应用与生物医药和食品包装领域。在目前提倡节能环保、绿色低碳的理念下,可完全降解回归自然的材料日益引起大家的关注。
中国专利CN103950257A公开了一种高阻隔生物基复合膜,复合膜最新采用PLA、PHA、PBS生物材料,但其阻隔层是PVDC、EVOH以及羟基类的其他树脂,阻隔层材料不可生物降解,对环保不友好,导致该专利的高阻隔生物基复合膜不能实现完全生物降解。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种耐热、低水蒸气透过率且可生物降解的纸塑复合材料及其制备方法和应用。
本发明的目的可以通过以下技术方案来实现:
本发明一方面提供一种耐热、低水蒸气透过率且可生物降解的纸塑复合材料,该纸塑复合材料以纸张为基材,以多层可降解薄膜为阻隔层;所述的多层可降解薄膜为PBS和改性PBAT形成的多层共挤膜,所述的改性PBAT中含有片状填料。
作为本发明优选的技术方案,所述的改性PBAT包括以下重量份含量的组分:
PBAT 80~120,
片状填料 5~20,
抗氧剂 0.2~1。
作为本发明优选的技术方案,所述的PBAT和片状填料的重量比为100:5~20;
作为本发明优选的技术方案,所述的PBAT和抗氧剂的重量比为100:0.3~0.6。
作为本发明优选的技术方案,所述的片状填料包括片层滑石粉和片状硅酸铝钾的一种或两种。
作为本发明优选的技术方案,所述的片状填料为片状硅酸铝钾。
作为本发明优选的技术方案,所述的抗氧剂为抗氧剂245、抗氧剂300、抗氧剂330、抗氧剂1010、抗氧剂168、抗氧剂264和抗氧剂1098中的一种或几种。进一步优选所述的抗氧剂为抗氧剂245、抗氧剂300和抗氧剂330中的一种或多种。更进一步优选所述的抗氧剂为抗氧剂245。
作为本发明优选的技术方案,所述的多层可降解薄膜包括PBS/改性PBAT/PBS共挤膜或PBS/改性PBAT共挤膜。
作为本发明优选的技术方案,所述的多层可降解薄膜的厚度为10~100μm。进一步优选多层可降解薄膜的厚度可根据需要在20-70μm调整。
作为本发明优选的技术方案,所述的PBS与PBAT薄膜层厚度之比为1:1~5。
作为本发明优选的技术方案,所述的PBAT和PBS可以选自现有技术中己公开的相应树脂。
作为本发明优选的技术方案,所述的片状填料(优选片状硅酸铝钾)选自现有技术中的片状硅酸铝钾。
本发明第二方面提供所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料的制备方法,包括以下步骤:
(1)PBAT改性加工:
将PBAT树脂和片状填料分别干燥后,加热挤出造粒,得到改性PBAT树脂颗粒;
(2)多层共挤吹膜:
将PBS树脂干燥,与步骤(1)制得的改性PBAT树脂颗粒,分别加入到对应的挤出机中,经过挤出机塑化和均化后的热熔物料经过多层模头拉伸吹胀后,得到多层预制膜,冷却后得到多层共挤膜;
(3)复合:
将步骤(2)得到的多层共挤膜通过水性复膜胶与纸张复合,得到所述的纸塑复合材料。
作为本发明优选的技术方案,步骤(1)中,PBAT树脂在80℃鼓风干燥箱中,烘干5小时进行干燥。
作为本发明优选的技术方案,步骤(1)中,片状填料在100℃真空干燥箱中,真空干燥2小时进行干燥。
作为本发明优选的技术方案,步骤(1)中,加热挤出造粒的温度为140~190℃;优选加热挤出造粒的温度为145~170℃,进一步优选加热挤出造粒过程中挤出造粒机分为五个温区,一区加热温度为145℃,二区加热温度为165℃,三区加热温度为170℃,四区加热温度为170℃,五区加热温度为160℃。
作为本发明优选的技术方案,步骤(1)中,挤出造粒过程中,加入抗氧剂。
作为本发明优选的技术方案,步骤(2)中,PBS树脂在80℃鼓风干燥箱中,烘干5小时进行干燥。
作为本发明优选的技术方案,步骤(2)中,PBS树脂挤出机温度130~190℃,模头温度175~190℃,螺杆速度40~80rpm,牵引速度6~10mpm;改性PBAT树脂颗粒挤出机温度140~170℃,模头温度150~165℃,螺杆速度40~80rpm,牵引速度6~10mpm。
作为本发明优选的技术方案,步骤(3)中,所述的纸张基材包括任意克重的卡纸或包纸原纸。
本发明第三方面提供所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料在包装材料上的应用。
与现有技术相比,本发明具有以下有益效果:
本发明的耐热、低水蒸气透过率且可生物降解的纸塑复合材料,PBAT经硅酸铝钾改性后具有很好的阻隔水蒸气性能,与PBS多层共挤不仅有良好的耐热性,而且纸塑包装还可以做到热压封合。本发明能够达到与传统PE、PP纸塑复合包装同样的阻隔水蒸气性能,可完全生物降解,环保性能强大,能够防止对环境的污染,可广泛应用于食品、医药制品等领域。
具体实施方式
下面结合具体实施例对本发明进行详细说明。
以下为实施例和对比例中的原料:
PBS树脂,泰国PTT MCC生产,牌号BioPBS FZ91PM;PBAT树脂,德国BASF,牌号ecovi1335。
实施例1
一种耐热、低水蒸气透过率且可生物降解的纸塑复合材料的制备方法:
(1)PBAT改性加工:
将PBAT树脂在80℃鼓风干燥箱中,烘干5小时,片状硅酸铝钾在100℃真空干燥箱中,真空干燥2小时。将81份PBAT、18.7份硅酸铝钾和0.3份抗氧剂245混合均匀加入双螺杆挤出机中,挤出造粒。
造粒机的加热条件为:一区加热温度为145℃,二区加热温度为165℃,三区加热温度为170℃,四区加热温度为170℃,五区加热温度为160℃。
(2)多层共挤吹膜:
将PBS树脂在80℃鼓风干燥箱中,烘干5小时,与步骤一制得的改性PBAT树脂颗粒,将物料分别加入到对应的挤出机中,复合薄膜挤出工艺参数分别为:PBS挤出机温度130~190℃,模头温度175℃,螺杆速度40rpm,牵引速度8mpm。PBAT挤出机温度140~170℃,模头温度150℃,螺杆速度40rpm,牵引速度8mpm。经过挤出机的塑化和均化后的热熔物料经过多层模头拉伸吹胀后得到PBS/改性PBAT/PBS三层预制膜,各层膜的厚度分别为10μm/20μm/10μm。冷却收卷后得到复合薄膜。薄膜厚度为40μm。
(3)复合:
将步骤(2)所制得的三层复合薄膜通过水性复膜胶与140g纸杯原纸复合,制得耐热、低水蒸气透过率且可生物降解的纸塑复合材料。
实施例2
一种耐热、低水蒸气透过率且可生物降解的纸塑复合材料的制备方法:
(1)PBAT改性加工:
将PBAT树脂在80℃鼓风干燥箱中,烘干5小时,片状硅酸铝钾在100℃真空干燥箱中,真空干燥2小时。将92份PBAT、7.8份硅酸铝钾和0.2份抗氧剂300混合均匀加入双螺杆挤出机中,挤出造粒。
造粒机的加热条件为:一区加热温度为145℃,二区加热温度为165℃,三区加热温度为170℃,四区加热温度为170℃,五区加热温度为160℃。
(2)多层共挤吹膜:
将PBS树脂在80℃鼓风干燥箱中,烘干5小时,与步骤一制得的改性PBAT树脂颗粒,将物料分别加入到对应的挤出机中,复合薄膜挤出工艺参数分别为:PBS挤出机温度130~190℃,模头温度175℃,螺杆速度60rpm,牵引速度10mpm。PBAT挤出机温度140~170℃,模头温度150℃,螺杆速度60rpm,牵引速度10mpm。经过挤出机的塑化和均化后的热熔物料经过多层模头拉伸吹胀后得到PBS/改性PBAT两层预制膜,各层膜的厚度分别为10μm/10μm。冷却收卷后得到复合薄膜。薄膜厚度为20μm。
(3)复合:
将步骤(2)所制得的两层复合薄膜通过水性复膜胶将PBAT面与红塔纸业SBS300g单涂白卡复合,制得耐热、低水蒸气透过率且可生物降解的纸塑复合材料。
对比例1
(1)纯PBAT吹膜:
将PBAT树脂在80℃鼓风干燥箱中,烘干5小时后加入到挤出机中,PBAT薄膜挤出工艺参数为:挤出机温度140~170℃,模头温度150℃,螺杆速度60rpm,牵引速度10mpm。经过挤出机的塑化和均化后的热熔物料经过模头拉伸吹胀后得到纯PBAT单层预制膜,冷却收卷后得到复合薄膜。薄膜厚度为40μm。
(2)复合:
将步骤(1)所制得的PBAT薄膜通过水性复膜胶与红塔纸业SBS300g单涂白卡复合,制得普通可生物降解的纸塑复合材料。
对比例2:
(1)多层共挤吹膜:
将PBS与PBAT树脂在80℃鼓风干燥箱中,烘干5小时,将两物料分别加入到对应的挤出机中,复合薄膜挤出工艺参数分别为:PBS挤出机温度130~190℃,模头温度175℃,螺杆速度60rpm,牵引速度10mpm。PBAT挤出机温度140~170℃,模头温度150℃,螺杆速度60rpm,牵引速度10mpm。经过挤出机的塑化和均化后的热熔物料经过多层模头拉伸吹胀后得到PBS/PBAT两层预制膜,冷却收卷后得到复合薄膜。薄膜厚度为20μm。
(2)复合:
将步骤(1)所制得的两层复合薄膜通过水性复膜胶将PBAT面与140g纸杯原纸复合,制得普通可生物降解的纸塑复合材料。
性能评价方式及实行标准:按GB/T1037-1988试验方法测试:
具体性能结果如表1所示。
表1
通过本方法制得的可生物降解的纸塑复合材料有水蒸气阻隔率高,耐热好(100℃沸水),表面光泽度也非常好,质地均匀,印刷性能好,热封性能好,对比例1、2与实施例形成对照,随着片状硅酸铝钾的加入,复合材料的水蒸气透过率大幅降低,有效解决了可生物降解系列薄膜高水蒸汽透过率的缺陷;且薄膜加工方法简单易行,有利于促进生物降解材料在包装方面的应用,节约能源,保护环境。
实施例3
一种耐热、低水蒸气透过率且可生物降解的纸塑复合材料的制备方法:
(1)PBAT改性加工:
将PBAT树脂在80℃鼓风干燥箱中,烘干5小时,片状硅酸铝钾在100℃真空干燥箱中,真空干燥2小时。将120份PBAT、5份硅酸铝钾和1份抗氧剂245混合均匀加入双螺杆挤出机中,在140~190℃下挤出造粒。
(2)多层共挤吹膜:
将PBS树脂在80℃鼓风干燥箱中,烘干5小时,与步骤一制得的改性PBAT树脂颗粒,将物料分别加入到对应的挤出机中,复合薄膜挤出工艺参数分别为:PBS挤出机温度130~190℃,模头温度190℃,螺杆速度80rpm,牵引速度6mpm。PBAT挤出机温度140~170℃,模头温度165℃,螺杆速度80rpm,牵引速度6mpm。经过挤出机的塑化和均化后的热熔物料经过多层模头拉伸吹胀后得到PBS/改性PBAT/PBS三层预制膜,冷却收卷后得到复合薄膜。薄膜厚度为100μm。
(3)复合:
将步骤(2)所制得的三层复合薄膜通过水性复膜胶与140g纸杯原纸复合,制得耐热、低水蒸气透过率且可生物降解的纸塑复合材料。
实施例4
一种耐热、低水蒸气透过率且可生物降解的纸塑复合材料的制备方法:
(1)PBAT改性加工:
将PBAT树脂在80℃鼓风干燥箱中,烘干5小时,片状硅酸铝钾在100℃真空干燥箱中,真空干燥2小时。将80份PBAT、20份硅酸铝钾和0.5份抗氧剂245混合均匀加入双螺杆挤出机中,在140~190℃下挤出造粒。
将PBS树脂在80℃鼓风干燥箱中,烘干5小时,与步骤一制得的改性PBAT树脂颗粒,将物料分别加入到对应的挤出机中,复合薄膜挤出工艺参数分别为:PBS挤出机温度130~190℃,模头温度180℃,螺杆速度60rpm,牵引速度10mpm。PBAT挤出机温度140~170℃,模头温度155℃,螺杆速度80rpm,牵引速度10mpm。经过挤出机的塑化和均化后的热熔物料经过多层模头拉伸吹胀后得到PBS/改性PBAT两层预制膜,冷却收卷后得到复合薄膜。薄膜厚度为10μm。
(3)复合:
将步骤(2)所制得的三层复合薄膜通过水性复膜胶与140g纸杯原纸复合,制得耐热、低水蒸气透过率且可生物降解的纸塑复合材料。
实施例5
本实施例与实施例1基本相同,不同之处在于,本实施例中,片状填料选择片层滑石粉。
实施例6
本实施例与实施例1基本相同,且本实施例中,抗氧剂选择抗氧剂245、抗氧剂300、抗氧剂330、抗氧剂1010、抗氧剂168、抗氧剂264或抗氧剂1098中的一种或几种任意比例的混合物。例如可以是抗氧剂300、抗氧剂330、抗氧剂1010、抗氧剂168、抗氧剂264或抗氧剂1098中的任一种。或者抗氧剂1010、抗氧剂168和抗氧剂264混合、抗氧化剂245和抗氧剂300混合等等,混合比例可以是任意的。
上述对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种耐热、低水蒸气透过率且可生物降解的纸塑复合材料,其特征在于,该纸塑复合材料以纸张为基材,以多层可降解薄膜为阻隔层;所述的多层可降解薄膜为PBS和改性PBAT形成的多层共挤膜,所述的改性PBAT中含有片状填料。
2.根据权利要求1所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料,其特征在于,所述的改性PBAT包括以下重量份含量的组分:
PBAT 80~120,
片状填料 5~20,
抗氧剂 0.2~1。
3.根据权利要求2所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料,其特征在于,包括以下条件中的任一项或多项:
(i)所述的PBAT和片状填料的重量比为100:5~20;
(ii)所述的PBAT和抗氧剂的重量比为100:0.3~0.6。
4.根据权利要求1或2所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料,其特征在于,所述的片状填料包括片层滑石粉和片状硅酸铝钾的一种或两种。
5.根据权利要求4所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料,其特征在于,所述的片状填料为片状硅酸铝钾。
6.根据权利要求2所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料,其特征在于:
所述的抗氧剂为抗氧剂245、抗氧剂300、抗氧剂330、抗氧剂1010、抗氧剂168、抗氧剂264和抗氧剂1098中的一种或几种;
优选地,所述的抗氧剂为抗氧剂245、抗氧剂300和抗氧剂330中的一种或多种;
进一步优选地,所述的抗氧剂为抗氧剂245。
7.根据权利要求1所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料,其特征在于,所述的多层可降解薄膜包括PBS/改性PBAT/PBS共挤膜或PBS/改性PBAT共挤膜。
8.如权利要求1~7任一所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料的制备方法,其特征在于,包括以下步骤:
(1)PBAT改性加工:
将PBAT树脂和片状填料分别干燥后,加热挤出造粒,得到改性PBAT树脂颗粒;
(2)多层共挤吹膜:
将PBS树脂干燥,与步骤(1)制得的改性PBAT树脂颗粒,分别加入到对应的挤出机中,经过挤出机塑化和均化后的热熔物料经过多层模头拉伸吹胀后,得到多层预制膜,冷却后得到多层共挤膜;
(3)复合:
将步骤(2)得到的多层共挤膜通过水性复膜胶与纸张复合,得到所述的纸塑复合材料。
9.如权利要求8所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料的制备方法,其特征在于,该方法包括以下条件中的任一项或多项:
(a)步骤(1)中,PBAT树脂在80℃鼓风干燥箱中,烘干5小时进行干燥;
(b)步骤(1)中,片状填料在100℃真空干燥箱中,真空干燥2小时进行干燥;
(c)步骤(1)中,加热挤出造粒的温度为140~190℃;优选加热挤出造粒的温度为145~170℃,进一步优选加热挤出造粒过程中挤出造粒机分为五个温区,一区加热温度为145℃,二区加热温度为165℃,三区加热温度为170℃,四区加热温度为170℃,五区加热温度为160℃;
(d)步骤(1)中,挤出造粒过程中,加入抗氧剂;
(e)步骤(2)中,PBS树脂在80℃鼓风干燥箱中,烘干5小时进行干燥;
(f)步骤(2)中,PBS树脂挤出机温度130~190℃,模头温度175~190℃,螺杆速度40~80rpm,牵引速度6~10mpm;改性PBAT树脂颗粒挤出机温度140~170℃,模头温度150~165℃,螺杆速度40~80rpm,牵引速度6~10mpm;
(g)步骤(3)中,所述的纸张基材包括任意克重的卡纸或包纸原纸。
10.如权利要求1~8任一所述的耐热、低水蒸气透过率且可生物降解的纸塑复合材料在包装材料上的应用。
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