CN112140494A - 一种可降解的生物降解膜制备方法 - Google Patents

一种可降解的生物降解膜制备方法 Download PDF

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CN112140494A
CN112140494A CN202010855192.XA CN202010855192A CN112140494A CN 112140494 A CN112140494 A CN 112140494A CN 202010855192 A CN202010855192 A CN 202010855192A CN 112140494 A CN112140494 A CN 112140494A
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film
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李清让
邓宗强
邓峰
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Hunan Kelaibao Bioenergy Technology Co ltd
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Abstract

本发明公开了一种可降解的生物降解膜制备方法,包括以下步骤:S1:准备原料:所述内层按重量份计:PBAT35份~95份、PLA0份~30份,生物降解材料10份~40份,淀粉0份~30份,无机粉体0份~30份,以及改性助剂0份~15份;该发明通过控制挤出机的工作状态不同,使得生产要求不同的内层膜、外层膜以及中层膜都可以被挤出得到,提高了吹膜的便捷性,通过三层或多层共挤,将PBAT基作为防水的内层和外层,同时将不耐水的PVA基材料作为中层降低成本,通过吹膜或流延膜的方法制膜,降低整体生物降解膜的成本。

Description

一种可降解的生物降解膜制备方法
技术领域
本发明具体涉及降解膜制备技术领域,尤其涉及一种可降解的生物降解膜制备方法。
背景技术
传统塑料大多性能稳定,在自然界中不易为各种环境因素的作用而迅速降解,以至于出现了废弃塑料对环境的严重危害,即所谓白色污染。随之,生物降解塑料被研发出来,生物降解塑料可以在短时间内被微生物侵蚀消化分解为二氧化碳、水、其它生物质和无机物,为环境低负荷材料。
PBAT是目前综合性能最佳的生物降解膜材料,但是存在价格高,全球产能小的问题。聚乙烯醇(PVA)也是一种具有较好生物降解性能的成膜原材料,但是由于其分子结构的氢键作用,其熔点与分解温度接近,无法热塑成型,只能通过水溶流延成膜,速度慢、能耗高、成本高。
经检索,中国专利公开号为CN110654095A的专利公开了一种生物降解膜及其制造方法,包括内层,中层,以及外层,所述中层设于所述内层与所述外层之间。利用上述专利方法生产出来的产品其降解能力还是不能满足人们的需求。
发明内容
本发明的目的是为了解决现有技术中存在的缺点,而提出的一种可降解的生物降解膜制备方法。
为了实现上述目的,本发明采用了如下技术方案:
一种可降解的生物降解膜制备方法,包括以下步骤:
S1:准备原料:
所述内层按重量份计:PBAT35份~95份、PLAO份~30份,生物降解材料10份~40份,淀粉0份~30份,无机粉体0份~30份,以及改性助剂0份~15份;
所述中层按重量份计:PBATO份~60份,PLA35份~95份,生物降解材料10份~40份,淀粉0份~30份,无机粉体0份~30份,以及改性助剂1份~15份;
所述外层按重量份计:PBAT40份~100份、PLAO份~35份,生物降解材料10份~40份,淀粉0份~30份,无机粉体0份~30份,以及改性助剂0份~15份;
S2:制取母料:将制取生物降解膜内层、外层以及中层所需的原料:PBAT,PLA,生物降解材料,淀粉、无机粉体以及改性助剂按照比例分别倒入三层共挤吹膜机的三个挤出机中预混,得到预混料;
S3:挤出薄膜:调整各个部分的机器参数,将预混料通过双螺杆挤出机进行熔融挤出,采用上吹法吹塑成膜,得到对应的三层共挤生物降解上吹薄膜;
S4:得到母料:将挤出的上吹薄膜,冷却,切粒,烘干得到对应的母料。
进一步的,所述生物降解材料为聚己内酯、聚丁二酸丁二醇酯及其共聚物、聚乳酸、聚羟基烷酸酯、脂肪族芳香族共聚酯或聚乙烯醇当中的一种或几种。
在前述方案的基础上,所述改性助剂包括至少一种具有至少两种指定官能团的化合物的相容剂;或包括至少一种具有至少两种指定官能团的化合物的交联剂;或包括至少一种具有至少两种指定官能团的化合物的扩链剂。
作为本发明再进一步的方案,所述指定官能团包括硅烷,钛酸酯,铝酸酯,异氰酸酯,过氧化物,碳二亚胺,异氰脲酸酯,噁唑啉,环氧化物,马来酸酐,以及二乙烯基醚基。
进一步的,所述S3中,挤出机的工作温度在120℃~200℃之间,机头温度在140℃-200℃之间,螺杆转速:20rpm-400rpm;牵引速度:5.5m/min-25.5m/min;吹胀比:1.5-3.0。
在前述方案的基础上,所述S3中,内层膜挤出时挤出机的工作温度在120℃~160℃之间,机头温度在140℃-180℃之间,螺杆转速:150rpm-300rpm。
作为本发明再进一步的方案,所述S3中,外层膜挤出时挤出机的工作温度在120℃~160℃之间,机头温度在140℃-180℃之间,螺杆转速:150rpm-300rpm。
进一步的,所述S3中,中层膜挤出时挤出机的工作温度在150℃~180℃之间,机头温度在170℃-200℃之间,螺杆转速:150rpm-300rpm。
本发明的有益效果为:
1.通过三层或多层共挤,将PBAT基作为防水的内层和外层,同时将不耐水的PVA基材料作为中层降低成本,通过吹膜或流延膜的方法制膜,降低整体生物降解膜的成本。
2.通过控制挤出机的工作状态不同,使得生产要求不同的内层膜、外层膜以及中层膜都可以被挤出得到,提高了吹膜的便捷性。
3.通过在增加生物降解材料来源在保证生物降解膜耐水性的前提下通过利用PVA(聚乙烯醇)材料,达到降低生物降解膜成本的目的。
附图说明
图1为本发明提出的一种可降解的生物降解膜制备方法的流程结构示意图;
图2为本发明提出的一种可降解的生物降解膜制备方法的结果对比图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
所述实施例的示例在附图中示出,其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的,仅用于解释本专利,而不能理解为对本专利的限制。
在本专利的描述中,需要说明的是,除非另有明确的规定和限定,术语“安装”、“相连”、“连接”、“设置”应做广义理解,例如,可以是固定相连、设置,也可以是可拆卸连接、设置,或一体地连接、设置。对于本领域的普通技术人员而言,可以根据具体情况理解上述术语在本专利中的具体含义。
实施例1
参照图1和图2,一种可降解的生物降解膜制备方法,包括以下步骤:
S1:准备原料:
所述内层按重量份计:PBAT 65份、PLA 15份,生物降解材料25份,淀粉15份,无机粉体15份,以及改性助剂10份;其中,无机粉体选用重质碳酸钙,改性助剂选用环氧扩链剂ADR-4370F1.5份,铝酸酯偶联剂DL4111.8份,加工润滑剂(乙撑双硬脂酰胺)1份,爽滑剂(芥酸酰胺)4.5份,热稳定剂(硬脂酸锌)1.2份;
所述中层按重量份计:PBAT 45份,PLA 60份,生物降解材料25份,淀粉15份,无机粉体15份,以及改性助剂10份;改性助剂为:加工润滑剂(乙撑双硬脂酰胺)0.5份,爽滑剂(芥酸酰胺)2.5份,抗氧化剂(受阻胺)1份,增塑剂(甘油)3份,增塑剂(甲酰胺)1.5份,增塑剂(无水氯化钙)1.5份;
所述外层按重量份计:PBAT 65份、PLA 25份,生物降解材料25份,淀粉15份,无机粉体15份,以及改性助剂10份;其中,无机粉体选用重质碳酸钙,改性助剂选用环氧扩链剂ADR-4370F1.5份,铝酸酯偶联剂DL411 1.8份,加工润滑剂(乙撑双硬脂酰胺)1份,爽滑剂(芥酸酰胺)4.5份,热稳定剂(硬脂酸锌)1.2份;
S2:制取母料:将制取生物降解膜内层、外层以及中层所需的原料:PBAT,PLA,生物降解材料,淀粉、无机粉体以及改性助剂按照比例分别倒入三层共挤吹膜机的三个挤出机中预混,得到预混料;
S3:挤出薄膜:调整各个部分的机器参数,将预混料通过双螺杆挤出机进行熔融挤出,采用上吹法吹塑成膜,得到对应的三层共挤生物降解上吹薄膜;
S3中,内层膜挤出时挤出机的工作温度在120℃,机头温度在140℃,螺杆转速:200rpm,S3中,外层膜挤出时挤出机的工作温度在120℃,机头温度在140℃,螺杆转速:1200rpm,S3中,中层膜挤出时挤出机的工作温度在150℃,机头温度在170℃,螺杆转速:200rpm;
S4:得到母料:将挤出的上吹薄膜,冷却,切粒,烘干得到对应的母料。
生物降解材料为聚己内酯、聚丁二酸丁二醇酯及其共聚物、聚乳酸、聚羟基烷酸酯、脂肪族芳香族共聚酯或聚乙烯醇当中的一种或几种。
改性助剂包括至少一种具有至少两种指定官能团的化合物的相容剂;或包括至少一种具有至少两种指定官能团的化合物的交联剂;或包括至少一种具有至少两种指定官能团的化合物的扩链剂,指定官能团包括硅烷,钛酸酯,铝酸酯,异氰酸酯,过氧化物,碳二亚胺,异氰脲酸酯,噁唑啉,环氧化物,马来酸酐,以及二乙烯基醚基。
S3中,挤出机的工作温度在120℃~200℃之间,机头温度在140℃-200℃之间,螺杆转速:20rpm-400rpm;牵引速度:5.5m/min-25.5m/min;吹胀比:1.5-3.0。
本实施例工作原理:通过复合增塑剂打破PVA分子及淀粉分子间氢键降低其熔点后,在双螺杆反应挤出过程热熔PVA与淀粉分子生成互穿网络结构并与聚乳酸形成合金,然后真空抽提大部分复合增塑剂循环使用,制备PVA基生物降解改性热塑性吹膜母料,本发明创新性的运用多层共挤技术以自主研发的熔体强度较高、热封合稳定、耐水性好的PBAT/PLA改性母料作为内外层,以PVA基生物降解改性热塑性吹膜母料中层吹膜制备完全生物降解多层共挤膜,解决PVA耐水性差的问题,以便通过加入PVA来生产成本更低、使原料来源更广泛、生物降解性能满足国家生物分解塑料标准。
实施例2
参照图1和图2,一种可降解的生物降解膜制备方法,包括以下步骤:
S1:准备原料:
所述内层按重量份计:PBAT 95份、PLA 30份,生物降解材料30份,淀粉30份,无机粉体30份,以及改性助剂10份;其中,无机粉体选用重质碳酸钙,改性助剂选用环氧扩链剂ADR-4370F1.5份,铝酸酯偶联剂DL4111.8份,加工润滑剂(乙撑双硬脂酰胺)1份,爽滑剂(芥酸酰胺)4.5份,热稳定剂(硬脂酸锌)1.2份;
所述中层按重量份计:PBAT 60份,PLA 95份,生物降解材料30份,淀粉30份,无机粉体30份,以及改性助剂10份;改性助剂为:加工润滑剂(乙撑双硬脂酰胺)0.5份,爽滑剂(芥酸酰胺)2.5份,抗氧化剂(受阻胺)1份,增塑剂(甘油)3份,增塑剂(甲酰胺)1.5份,增塑剂(无水氯化钙)1.5份
所述外层按重量份计:PBAT 100份、PLA 35份,生物降解材料40份,淀粉30份,无机粉体30份,以及改性助剂10份;其中,无机粉体选用重质碳酸钙,改性助剂选用环氧扩链剂ADR-4370F1.5份,铝酸酯偶联剂DL411 1.8份,加工润滑剂(乙撑双硬脂酰胺)1份,爽滑剂(芥酸酰胺)4.5份,热稳定剂(硬脂酸锌)1.2份;
S2:制取母料:将制取生物降解膜内层、外层以及中层所需的原料:PBAT,PLA,生物降解材料,淀粉、无机粉体以及改性助剂按照比例分别倒入三层共挤吹膜机的三个挤出机中预混,得到预混料;
S3:挤出薄膜:调整各个部分的机器参数,将预混料通过双螺杆挤出机进行熔融挤出,采用上吹法吹塑成膜,得到对应的三层共挤生物降解上吹薄膜;
S3中,内层膜挤出时挤出机的工作温度在160℃,机头温度在180℃,螺杆转速:300rpm,S3中,外层膜挤出时挤出机的工作温度在160℃,机头温度在180℃,螺杆转速:300rpm,S3中,中层膜挤出时挤出机的工作温度在180℃,机头温度在200℃,螺杆转速:300rpm;
S4:得到母料:将挤出的上吹薄膜,冷却,切粒,烘干得到对应的母料。
生物降解材料为聚己内酯、聚丁二酸丁二醇酯及其共聚物、聚乳酸、聚羟基烷酸酯、脂肪族芳香族共聚酯或聚乙烯醇当中的一种或几种。
改性助剂包括至少一种具有至少两种指定官能团的化合物的相容剂;或包括至少一种具有至少两种指定官能团的化合物的交联剂;或包括至少一种具有至少两种指定官能团的化合物的扩链剂,指定官能团包括硅烷,钛酸酯,铝酸酯,异氰酸酯,过氧化物,碳二亚胺,异氰脲酸酯,噁唑啉,环氧化物,马来酸酐,以及二乙烯基醚基。
S3中,挤出机的工作温度在120℃~200℃之间,机头温度在140℃-200℃之间,螺杆转速:20rpm-400rpm;牵引速度:5.5m/min-25.5m/min;吹胀比:1.5-3.0。
本实施例与实施例1的区别在于更换了原料的比重,观察该方法的生产效果。
通过复合增塑剂打破PVA分子及淀粉分子间氢键降低其熔点后,在双螺杆反应挤出过程热熔PVA与淀粉分子生成互穿网络结构并与聚乳酸形成合金,然后真空抽提大部分复合增塑剂循环使用,制备PVA基生物降解改性热塑性吹膜母料,本发明创新性的运用多层共挤技术以自主研发的熔体强度较高、热封合稳定、耐水性好的PBAT/PLA改性母料作为内外层,以PVA基生物降解改性热塑性吹膜母料中层吹膜制备完全生物降解多层共挤膜,解决PVA耐水性差的问题,以便通过加入PVA来生产成本更低、使原料来源更广泛、生物降解性能满足国家生物分解塑料标准。
在本专利的描述中,需要理解的是,术语“中心”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系,仅是为了便于描述本专利和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本专利的限制。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。

Claims (8)

1.一种可降解的生物降解膜制备方法,其特征在于,包括以下步骤:
S1:准备原料:
所述内层按重量份计:PBAT35份~95份、PLAO份~30份,生物降解材料10份~40份,淀粉0份~30份,无机粉体0份~30份,以及改性助剂0份~15份;
所述中层按重量份计:PBATO份~60份,PLA35份~95份,生物降解材料10份~40份,淀粉0份~30份,无机粉体0份~30份,以及改性助剂1份~15份;
所述外层按重量份计:PBAT40份~100份、PLAO份~35份,生物降解材料10份~40份,淀粉0份~30份,无机粉体0份~30份,以及改性助剂0份~15份;
S2:制取母料:将制取生物降解膜内层、外层以及中层所需的原料:PBAT,PLA,生物降解材料,淀粉、无机粉体以及改性助剂按照比例分别倒入三层共挤吹膜机的三个挤出机中预混,得到预混料;
S3:挤出薄膜:调整各个部分的机器参数,将预混料通过双螺杆挤出机进行熔融挤出,采用上吹法吹塑成膜,得到对应的三层共挤生物降解上吹薄膜;
S4:得到母料:将挤出的上吹薄膜,冷却,切粒,烘干得到对应的母料。
2.如权利要求1所述的一种可降解的生物降解膜制备方法,其特征在于:所述生物降解材料为聚己内酯、聚丁二酸丁二醇酯及其共聚物、聚乳酸、聚羟基烷酸酯、脂肪族芳香族共聚酯或聚乙烯醇当中的一种或几种。
3.如权利要求1所述的一种可降解的生物降解膜制备方法,其特征在于:所述改性助剂包括至少一种具有至少两种指定官能团的化合物的相容剂;或包括至少一种具有至少两种指定官能团的化合物的交联剂;或包括至少一种具有至少两种指定官能团的化合物的扩链剂。
4.如权利要求3所述的一种可降解的生物降解膜制备方法,其特征在于:指定官能团包括硅烷,钛酸酯,铝酸酯,异氰酸酯,过氧化物,碳二亚胺,异氰脲酸酯,噁唑啉,环氧化物,马来酸酐,以及二乙烯基醚基。
5.如权利要求1所述的一种可降解的生物降解膜制备方法,其特征在于:所述S3中,挤出机的工作温度在120℃~200℃之间,机头温度在140℃-200℃之间,螺杆转速:20rpm-400rpm;牵引速度:5.5m/min-25.5m/min;吹胀比:1.5-3.0。
6.如权利要求1所述的一种可降解的生物降解膜制备方法,其特征在于:所述S3中,内层膜挤出时挤出机的工作温度在120℃~160℃之间,机头温度在140℃-180℃之间,螺杆转速:150rpm-300rpm。
7.如权利要求1所述的一种可降解的生物降解膜制备方法,其特征在于:所述S3中,外层膜挤出时挤出机的工作温度在120℃~160℃之间,机头温度在140℃-180℃之间,螺杆转速:150rpm-300rpm。
8.如权利要求1所述的一种可降解的生物降解膜制备方法,其特征在于:所述S3中,中层膜挤出时挤出机的工作温度在150℃~180℃之间,机头温度在170℃-200℃之间,螺杆转速:150rpm-300rpm。
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CN113861659A (zh) * 2021-10-09 2021-12-31 南京五瑞生物降解新材料研究院有限公司 一种生物基可降解膜及制备工艺
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