CN102181077B - 一种符合en13432标准的全生物降解薄膜及制备方法 - Google Patents

一种符合en13432标准的全生物降解薄膜及制备方法 Download PDF

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CN102181077B
CN102181077B CN2011100604120A CN201110060412A CN102181077B CN 102181077 B CN102181077 B CN 102181077B CN 2011100604120 A CN2011100604120 A CN 2011100604120A CN 201110060412 A CN201110060412 A CN 201110060412A CN 102181077 B CN102181077 B CN 102181077B
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polyvinyl alcohol
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CN102181077A (zh
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冯硕
杨育军
路连峰
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Zhuhai hailanxing polymer material Co.,Ltd.
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29B7/82Heating or cooling
    • B29B7/823Temperature control
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B29B7/80Component parts, details or accessories; Auxiliary operations
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29B9/00Making granules
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Abstract

本发明涉及一种符合EN13432标准的全生物降解薄膜及制备方法。本发明的主要配方成份为淀粉与聚乙烯醇,淀粉在自然界中可生物分解,聚乙烯醇在自然界可以通过水解和生物降解两种途径分解,最终分解产物为H-2O和CO-2,无色、无味、无毒、无害,达到EN13432的检测要求,彻底改变了传统塑料包装材料和现有的可降解包装材料对环境的破坏和影响;另一方面,通过改变生产工艺和设备,使薄膜中的淀粉含量提高,使整体材料的成本低于传统塑料,从根本上替代或部分替代传统塑料包装材料,彻底解决“白色污染”的难题;本发明应用范围广泛,可用于垃圾分类和沼气/堆肥处理的餐厨垃圾袋、要求完全生物降解的购物袋、干货包装袋、书报袋等。

Description

一种符合EN13432标准的全生物降解薄膜及制备方法
技术领域
本发明涉及生物降解材料技术领域,尤其是一种符合EN13432标准的全生物降解薄膜及制备方法。
背景技术
生物降解材料是世界上各国重点研究的环保课题。目前国内采用以聚乙烯醇为聚合树脂来开发生物降解包装材料的单位,因其聚乙烯醇含量高于30%的原因,无法达到EN13432标准所规定的180天降解和12周崩解90%的指标,因而也无法进入国际主流销售市场;单纯降低聚乙烯醇的含量,成膜困难。目前,国内还没有出现以聚乙烯醇为聚合树脂的符合EN13432标准的全生物降解薄膜及制备方法。
发明内容
针对以上现有的可降解包装材料的不足,本发明的目的是提供一种符合EN13432标准的全生物降解薄膜及制备方法。
本发明的目的是通过采用以下技术方案来实现的:
一种符合EN13432标准的全生物降解薄膜,其按照质量百分比包括:
改性淀粉70-80%;
聚合树脂10-15%,其中,聚乙烯醇5-10%;
丙三醇10%;
复合助剂5%,其包括:增塑剂、分散剂、脱模剂、增强剂;
氧化剂0.5-1%;如氧化生物降解添加剂;
碳酰胺0.5-1%。
作为本发明优选的技术方案,所述改性淀粉为非转基因玉米淀粉、转基因玉米淀粉、木薯淀粉、甘薯淀粉或马铃薯淀粉。
一种符合EN13432标准的全生物降解薄膜的制备方法,其包括以下步骤:
第一步:称取配方量的聚乙烯醇,将聚乙烯醇进行预增塑处理生成改性聚乙烯醇,以降低其熔点;
第二步:称取配方量的改性淀粉,将其经淀粉细化机细化为1000目以上的改性细化淀粉颗粒;
第三步:称取与聚乙烯醇等量的去离子水、配方量的碳酰胺、氧化剂,将碳酰胺和氧化剂放入去离子水中,搅拌成为水溶液;
第四步:将水溶液、改性细化淀粉、改性聚乙烯醇都加入混料机中混合均匀;
第五步:称取配方量的丙三醇进行搅拌,边搅拌边加入第四步所得混合物料,然后再高速搅拌10分钟;
第六步:称取配方量的复合助剂,将其加入第五步所得混合物中,搅拌均匀,将搅拌后的物料放入高低温混料机的低温混料仓继续搅拌15分钟,出仓;
第七步:提供一中频加热双螺杆挤出机,将第六步搅拌好的物料放入该中频加热双螺杆挤出机上料斗内,设置中频加热双螺杆挤出机的十三个温区的温度,物料由喂料斗螺旋上料,经双螺杆喂料器均匀加入挤出机内,经高温高压挤出切粒,冷却,称重,包装;
第八步:提供一内冷循环吹膜机,将其预热备用,设置该内冷循环吹膜机各温区的温度,将制得粒料放入吹膜机料仓内,吹膜、牵引、收卷。
作为本发明优选的技术方案,所述中频加热双螺杆挤出机螺杆的长度与直径之比大于52。
作为本发明优选的技术方案,所述中频加热双螺杆挤出机的十三个温区分别设置不同的温度范围。
作为本发明优选的技术方案,所述中频加热双螺杆挤出机的十三个温区的温度分别设置为:
第一温区:60-80℃;
第二温区:80-100℃;
第三温区:100-120℃;
第四温区:160-180℃;
第五温区:160-180℃;
第六温区:200-220℃;
第七温区:200-220℃;
第八温区:250-260℃;
第九温区:200-220℃;
第十温区:180-200℃;
第十一温区:160-180℃;
第十二温区;130-150℃;
模头温区;120-140℃。
作为本发明优选的技术方案,所述内冷循环吹膜机的模头吹胀比为1:6。
作为本发明优选的技术方案,所述内冷循环吹膜机各温区的温度设置如下:
第一温区:120-150℃;
第二温区:150-180℃;
第三温区:120-150℃;
第四温区:100-130℃;
模头温区:100-120℃。
相对于现有技术,本发明的主要配方成份为淀粉与聚乙烯醇,淀粉在自然界中可生物分解,而聚乙烯醇在自然界可以通过水解和生物降解两种途径分解,最终分解产物为H-2O和CO-2,其水溶物无色、无味、无毒、无害,渗入土壤还可作为土壤改良剂, 达到EN13432的检测要求,彻底改变了传统塑料包装材料和现有的可降解包装材料对环境的破坏和影响;另一方面,通过改变生产工艺和设备,由于提高了淀粉的含量,从而使整体材料的成本低于传统塑料,从根本上替代或部分替代传统塑料包装材料,以彻底解决“白色污染”的难题;本发明应用范围广,可用于垃圾分类和沼气/堆肥处理的餐厨垃圾袋、要求完全生物降解的购物袋、干货包装袋、书报袋、狗屎袋、卫生巾带、服装以及工业包装材料等等。
具体实施方式
一、    本发明符合EN13432标准的全生物降解薄膜的配方(以质量百分比计):
改性淀粉70-80%;
聚合树脂10-15%,其中,聚乙烯醇5-10%;
丙三醇10%;
复合助剂5%,包括:增塑剂、分散剂、脱模剂、增强剂;
氧化剂0.5-1%,如氧化生物降解添加剂;
碳酰胺0.5-1%。
所述改性淀粉为非转基因玉米淀粉、转基因玉米淀粉、木薯淀粉、甘薯淀粉或马铃薯淀粉。
二、本发明符合EN13432标准的全生物降解薄膜的制备方法实施例包括以下步骤:
第一步:按重量称取聚乙烯醇100份,将聚乙烯醇进行预增塑处理生成改性聚乙烯醇,以降低其熔点;
第二步:按重量称取改性淀粉700份,将其经淀粉细化机细化为1000目以上的颗粒;
第三步:按重量称取去离子水100份、碳酰胺5份、氧化剂5份,将碳酰胺和氧化剂放入去离子水中,搅拌成为水溶液;
第四步:将水溶液、改性细化淀粉、改性聚乙烯醇都加入混料机中混合均匀;
第五步:按重量称取丙三醇100份进行搅拌,边搅拌边加入第四步所得混合物料,然后再高速搅拌10分钟;
第六步:按重量称取复合助剂50份,将其加入第五步所得混合物中,搅拌均匀,将搅拌后的物料放入高低温混料机的低温混料仓继续搅拌15分钟,出仓;
第七步:提供一中频加热双螺杆挤出机,将第六步搅拌好的物料放入该中频加热双螺杆挤出机上料斗内,中频加热双螺杆挤出机的十三个温区按以下温度设置:
第一温区:60-80℃;
第二温区:80-100℃;
第三温区:100-120℃;
第四温区:160-180℃;
第五温区:160-180℃;
第六温区;200-220℃;
第七温区:200-220℃;
第八温区:250-260℃;
第九温区:200-220℃;
第十温区:180-200℃;
第十一温区:160-180℃;
第十二温区:130-150℃;
模头温区:120-140℃;
物料由喂料斗螺旋上料,经双螺杆喂料器均匀加入挤出机内,经高温高压挤出切粒,冷却,称重,包装;
第八步:提供一内冷循环吹膜机,将其预热备用,该内冷循环吹膜机各温区的温度设定如下:
第一温区:120-150℃;
第二温区:150-180℃;
第三温区:120-150℃;
第四温区:100-130℃;
模头温区:100-120℃;
将制得粒料放入吹膜机料仓内,按照传统工艺流程吹膜、牵引、收卷。
三、设备:
1、中频加热双螺杆挤出机
本发明所述中频加热双螺杆挤出机设置13个温区,均采用中频加热方式,温度上升快,节电可靠,便于控制,温度控制精度在正负1度。螺杆的长度与直径之比大于52,螺杆的对应喂料部分设有进料口,塑化部分从前至后分为喂料化学反应段、混炼段和挤出段,喂料化学反应段为螺杆长度的40%,混炼段长度为螺杆长度的50%,挤出段长度为螺杆长度的10%。通过螺杆捏合块的组配,增加了剪切及混合,13个温区采用不同温度的设置,使得淀粉树脂与改性聚乙烯醇共混体系的各组分有机地熔合在一起,从而塑化更均匀。
2、内冷循环吹膜机的模头吹胀比为1:6,采用本发明所述按配方生产的粒料,在吹膜机产生膜泡的时候,无论横向或纵向都得到有效的的拉伸,内冷循环的作用可以使膜泡尽快结晶,从而使成膜质量得到提高。

Claims (6)

1.一种符合EN13432标准的全生物降解薄膜的制备方法,其特征是:包括以下步骤:
第一步:按质量称取5-10%的聚乙烯醇,将聚乙烯醇进行预增塑处理生成改性聚乙烯醇,以降低其熔点;
第二步:按质量称取70-80%的改性淀粉,将其经淀粉细化机细化为1000目以上的改性细化淀粉颗粒;
第三步:按质量称取与聚乙烯醇等量的去离子水、0.5-1%的碳酰胺、0.5-1%的氧化剂,将碳酰胺和氧化剂放入去离子水中,搅拌成为水溶液;
第四步:将水溶液、改性细化淀粉、改性聚乙烯醇都加入混料机中混合均匀;
第五步:按质量称取10%的丙三醇进行搅拌,边搅拌边加入第四步所得混合物料,然后再高速搅拌10分钟;
第六步:按质量称取5%的复合助剂,所述复合助剂为增塑剂、分散剂、脱模剂、增强剂,将其加入第五步所得混合物中,搅拌均匀,将搅拌后的物料放入高低温混料机的低温混料仓继续搅拌15分钟,出仓;
第七步:提供一中频加热双螺杆挤出机,将第六步搅拌好的物料放入该中频加热双螺杆挤出机上料斗内,设置中频加热双螺杆挤出机的十三个温区的温度,物料由喂料斗螺旋上料,经双螺杆喂料器均匀加入挤出机内,经高温高压挤出切粒,冷却,称重,包装;
第八步:提供一内冷循环吹膜机,将其预热备用,设置该内冷循环吹膜机各温区的温度,将制得粒料放入吹膜机料仓内,吹膜、牵引、收卷。
2.根据权利要求1所述的一种符合EN13432标准的全生物降解薄膜的制备方法,其特征是:所述中频加热双螺杆挤出机螺杆的长度与直径之比大于52。
3.根据权利要求1所述的一种符合EN13432标准的全生物降解薄膜的制备方法,其特征是:所述中频加热双螺杆挤出机的十三个温区分别设置不同的温度范围。
4.根据权利要求3所述的一种符合EN13432标准的全生物降解薄膜的制备方法,其特征是:所述中频加热双螺杆挤出机的十三个温区的温度分别设置为:
第一温区:60-80℃;
第二温区:80-100℃;
第三温区:100-120℃;
第四温区:160-180℃;
第五温区:160-180℃;
第六温区:200-220℃;
第七温区:200-220℃;
第八温区:250-260℃;
第九温区:200-220℃;
第十温区:180-200℃;
第十一温区:160-180℃;
第十二温区;130-150℃;
模头温区;120-140℃。
5.根据权利要求1所述的一种符合EN13432标准的全生物降解薄膜的制备方法,其特征是:所述内冷循环吹膜机的模头吹胀比为1:6。
6.根据权利要求1所述的一种符合EN13432标准的全生物降解薄膜的制备方法,其特征是:所述内冷循环吹膜机各温区的温度设置如下:
第一温区:120-150℃;
第二温区:150-180℃;
第三温区:120-150℃;
第四温区:100-130℃;
模头温区:100-120℃。
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