CN116874912B - 一种可降解膜及其制备方法 - Google Patents
一种可降解膜及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种可降解膜及其制备方法,所述可降解膜包括以下重量份数的组分:高密度聚乙烯10~15份、低密度聚乙烯22~34份、聚乳酸5~10份、聚乙交酯2~7份、棉秆细粉23~37份、变性淀粉12~22份、分散剂4~9份、增塑剂1~5份和表面活性剂1~3份;其中,所述棉秆细粉的制备方法为:将棉花秆磨碎至0.5~1.5mm,加入改性剂常温搅拌3~4h,所述棉花秆和改性剂的重量比为100:3~11。本制备的可降解膜,力学性能优异,透光率高、保水性好,可以大范围推广使用,尤其适用于西北地区使用。本发明的制备方法简单,易于操作,产品的品质统一性好,使用效果佳。
Description
技术领域
本发明属于可降解膜技术领域,具体涉及一种可降解膜及其制备方法。
背景技术
膜材料因性能稳定、价格低廉、使用轻便等优势,广泛应用于医疗、包装、化工、农业等领域。农用膜是继种子、化肥、农药之后的农业重要生产资料,它的应用为农业生产带来了一场革命,对农业增效、农民增收作出了重要贡献,农用膜现已普遍用于日光温室、蔬菜大棚和地面覆盖种植的覆盖材料。它主要包括棚膜和地膜、饲草用膜、遮阳网、防虫网等现代农用覆盖材料。然而,现有的膜材料大多为石油基制品,由于其相对分子量大、疏水性强、分子键稳定等,在自然界中通常需要100~200年甚至更长时间才能降解。与废旧膜材料回收处理相比,使用可降解膜替代传统不可降解膜成为缓解废旧膜材料污染的有效措施。并且随着我国栽培要求的不断提高,农用覆盖材料还达不到栽培更高的要求。CN113308936B公开了一种天然矿物纤维/植物纤维可降解农用地膜的制备方法,将天然矿物纤维进行表面改性后与天然植物纤维混合采用湿法造纸工艺制备可降解农用复合地膜。但该膜的透光率较差,并且其制备方法复杂,受原料天然矿物纤维的影响品质不易控。
发明内容
本发明的目的是提供一种新型可降解膜及其制备方法,制得的可降解膜的力学性能优异,透光率高、保水性好。
为了实现上述目的,本发明提供了以下技术方案:
一种可降解膜,包括以下重量份数的组分:高密度聚乙烯10~15份、低密度聚乙烯22~34份、聚乳酸5~10份、聚乙交酯2~7份、棉秆细粉23~37份、变性淀粉12~22份、分散剂4~9份、增塑剂1~5份和表面活性剂1~3份;其中,所述棉秆细粉的制备方法为:将棉花秆磨碎至0.5~1.5mm,加入改性剂常温搅拌3~4h,所述棉花秆和改性剂的重量比为100:3~11。
为了提高树脂基料彼此的相容性,优选的,所述高密度聚乙烯,购自默克,1546707;低密度聚乙烯,购自默克,GF56362642;所述聚乳酸的平均重均分子量60000,购自默克,38534;聚乙交酯的转变温度Tm 220-230℃,在0.1%(w/v)在六氟异丙醇(25℃)中固有粘度1.1-1.7dL/g,购自默克457620。
在一种优选的实施方式中,所述改性剂包括硅烷偶联剂、石蜡和丙烯酸。
在一种优选的实施方式中,所述硅烷偶联剂、石蜡和丙烯酸的重量比为(1~5):1:(0.1~0.3)。
现有技术中往往会在树脂基料中加入一定量的填料以期提高膜的力学性能,但在实际生产中会存在填料与树脂基料相容性不佳、膜表面有颗粒感、填料易析出等问题。本发明通过将棉杆细粉进行改性,增加其疏水性,改善与高密度聚乙烯、低密度聚乙烯、聚乳酸、聚乙交酯的相容性,提高可降解膜的力学性能。但是在研发过程中发现,添加棉杆细粉后,透光率有所下降,可能是棉杆细粉中的木质素中具有发色基团,导致膜的颜色较深。发明人发现通过添加重量比为(1~5):1:(0.1~0.3)硅烷偶联剂、石蜡和丙烯酸,可以提高可降解膜的透光率。猜测是丙烯酸可以使木质素中的发色基团的键发生开裂,在重新闭环时构型发生变化,降低发色基团对膜颜色的影响,同时,石蜡可以调节棉杆细粉纤维素、半纤维素、木质素之间的作用力,促进其与硅烷偶联剂的交联,使发色基团和助色基团结构产生变化。
为了提升可降解膜的保温性,在一种优选的实施方式中,所述棉杆细粉占高密度聚乙烯和低密度聚乙烯总重量的百分数大于60%。
在一种优选的实施方式中,所述增塑剂选自C原子数3~8的多元醇。
在我国西北部某些地区冬季温度非常低,因此这些地区对室外的农用膜脆化温度要求较高,而现有的农用膜在低温下使用经常会产生开裂现象。申请人发现使用C原子数3~8的多元醇作为增塑剂,可降低降解膜的脆化温度。猜测是该C原子数3~8的多元醇可以有效调节本发明体系中聚合物之间的范德华力,增加了聚合物分子链的移动性,降低了聚合物分子链的结晶性,增加了可降解膜的塑性。
在一种优选的实施方式中,所述变性淀粉选自酶法变性淀粉。
在一种优选的实施方式中,所述酶法变性淀粉选自α-环状糊精、β-环状糊精、γ-环状糊精、麦芽糊精、直链淀粉中的一种或多种。
为了增加可降解膜的稳定性,在一种优选的实施方式中,所述分散剂选自硬脂酸、油酸酰胺、芥酸酰胺、硬脂酸钙中的一种或多种。
在一种优选的实施方式中,所述表面活性剂为椰油基羟乙基磺酸钠、月桂基葡萄糖羧酸钠和椰油酰胺基丙基甜菜碱复配。
优选的,所述椰油基羟乙基磺酸钠、月桂基葡萄糖羧酸钠和椰油酰胺基丙基甜菜碱的重量比为1:(0.5~1):(3~7)。
在实际使用时,申请人发现在我国西北部等地区,由于气候的原因,可降解膜不能很好的保水,不利于植物的存活和生长。在经过大量的配方调试后,申请人发现增加表面活性剂可以降低可降解膜的水蒸汽透过率。猜测是表面活性剂可以提高膜的延展性,同时促进了变性淀粉与高分子聚合物的交联。进一步发现使用椰油基羟乙基磺酸钠、月桂基葡萄糖羧酸钠和椰油酰胺基丙基甜菜碱的重量比为1:(0.5~1):(3~7)作为表面活性剂,可降解膜的保水性更好。猜测是该配比的表面活性剂与分散剂、增塑剂协同发挥作用,调节了可降解膜的致密性。
本发明还提供了所述一种可降解膜的制备方法,所述制备方法包括以下步骤:将高密度聚乙烯、低密度聚乙烯、聚乳酸、聚乙交酯、棉秆细粉、变性淀粉、分散剂、增塑剂和表面活性剂混合均匀得混合物料;然后将混合物料放入双螺杆挤出机中熔融共混后130~150℃挤出,即得所述可降解膜。
与现有技术相比,本发明的优点和有益效果为:
1.本发明提供一种新型可降解膜,力学性能优异,稳定性高、透光率高、保水性好,可以在全国大范围推广使用,尤其适用于西北地区使用。
2.本发明通过将棉杆细粉进行改性,增加其疏水性,改善与高密度聚乙烯、低密度聚乙烯、聚乳酸、聚乙交酯的相容性,提高可降解膜的力学性能和防水性能。
3.本发明使用C原子数3~8的多元醇作为增塑剂,可降低降解膜的脆化温度。
4.本发明通过添加表面活性剂可以降低膜的水蒸汽透过率。
5.本发明的制备方法简单,易于操作,产品的品质统一性好。
具体实施方式
下面将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。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
以下实施例中的原料购自以下厂家:
高密度聚乙烯默克,1546707
低密度聚乙烯默克,GF56362642
聚乳酸默克,38534
聚乙交酯默克,457620
硅烷偶联剂KH550青岛恒达新材料科技有限公司
石蜡默克,327212
α-环状糊精默克,C4642
麦芽糊精默克,419699
直链淀粉默克,A0512
硬脂酸钙默克,V900174
椰油基羟乙基磺酸钠武汉华翔科洁生物技术有限公司
月桂基葡萄糖羧酸钠巴斯夫
椰油酰胺基丙基甜菜碱山东省博兴县昊隆化工有限公司
实施例1
本实施例提供了一种可降解膜,包括以下重量份数的组分:高密度聚乙烯14份、低密度聚乙烯28份、聚乳酸7份、聚乙交酯4份、棉秆细粉30份、变性淀粉17份、分散剂6份、增塑剂3份和表面活性剂2份;其中,所述棉秆细粉的制备方法为:将棉花秆磨碎至0.5~1.5mm,加入改性剂常温搅拌3.5h,所述棉花秆和改性剂的重量比为100:7。
所述改性剂包括硅烷偶联剂KH550、石蜡和丙烯酸。
所述硅烷偶联剂KH550、石蜡和丙烯酸的重量比为3:1:0.2。
所述增塑剂为重量比为1:1的丙三醇和山梨糖醇。
所述酶法变性淀粉为重量比为1:2:1的α-环状糊精、麦芽糊精、直链淀粉复配。
所述分散剂为硬脂酸钙。
所述表面活性剂为椰油基羟乙基磺酸钠、月桂基葡萄糖羧酸钠和椰油酰胺基丙基甜菜碱复配。
所述椰油基羟乙基磺酸钠、月桂基葡萄糖羧酸钠和椰油酰胺基丙基甜菜碱的重量比为1:0.7:5。
本发明还提供了所述一种可降解膜的制备方法,所述制备方法包括以下步骤:将高密度聚乙烯、低密度聚乙烯、聚乳酸、聚乙交酯、棉秆细粉、变性淀粉、分散剂、增塑剂和表面活性剂混合均匀得混合物料;然后将混合物料放入双螺杆挤出机中熔融共混后145℃挤出,即得所述可降解膜。
实施例2
本实施例与实施例1的不同在于:一种可降解膜,包括以下重量份数的组分:高密度聚乙烯10份、低密度聚乙烯34份、聚乳酸5份、聚乙交酯3份、棉秆细粉23份、变性淀粉22份、分散剂4份、增塑剂5份和表面活性剂2份。
实施例3
本实施例与实施例1的区别为:所述棉秆细粉的制备方法为:将棉花秆磨碎至0.5~1.5mm,加入改性剂常温搅拌3h,所述棉花秆和改性剂的重量比为100:9。所述改性剂为硅烷偶联剂KH550。
实施例4
本实施例与实施例1的区别为:所述硅烷偶联剂、石蜡和丙烯酸的重量比为0.3:1:5。
实施例5
本实施例与实施例1的区别为:高密度聚乙烯15份、低密度聚乙烯22份、聚乳酸2份、聚乙交酯8份、棉秆细粉40份、变性淀粉12份、分散剂6份、增塑剂3份和表面活性剂2份。
实施例6
本实施例与实施例1的区别为:所述增塑剂为重量比为1:1的乙二醇和丙三醇。
实施例7
本实施例与实施例1的区别为:所述表面活性剂为辛醇聚氧乙烯醚、十二烷基乙氧基磺基甜菜碱和椰油酰胺基丙基甜菜碱复配,重量比为1:3:1。
实施例8
本实施例与实施例1的区别为:一种可降解膜,包括以下重量份数的组分:高密度聚乙烯21份、低密度聚乙烯32份、棉秆细粉30份、变性淀粉17份、分散剂6份、增塑剂3份和表面活性剂2份。
性能测试
参照GB/T 4455-2019,测定实施例制备的可降解膜的力学性能和降解时间;参照GB/T 2410-2008测试实施例制备的可降解膜60μm厚度时的透光率;参照GB/T 16928,测定实施例制备的可降解膜60μm厚度时的透水性,设定流量时间为98s。结果见表1。
表1性能测试结果
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明所述原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (1)
1.一种可降解膜,其特征在于,包括以下重量份数的组分:高密度聚乙烯14份、低密度聚乙烯28份、聚乳酸7份、聚乙交酯4份、棉秆细粉30份、变性淀粉17份、分散剂6份、增塑剂3份和表面活性剂2份;其中,所述棉秆细粉的制备方法为:将棉花秆磨碎至0.5~1.5mm,加入改性剂常温搅拌3.5h,所述棉花秆和改性剂的重量比为100:7;
所述改性剂包括硅烷偶联剂KH550、石蜡和丙烯酸,所述硅烷偶联剂KH550、石蜡和丙烯酸的重量比为3:1:0.2;
所述增塑剂为重量比为1:1的丙三醇和山梨糖醇;
所述酶法变性淀粉为重量比为1:2:1的α-环状糊精、麦芽糊精、直链淀粉复配;
所述分散剂为硬脂酸钙;
所述表面活性剂为椰油基羟乙基磺酸钠、月桂基葡萄糖羧酸钠和椰油酰胺基丙基甜菜碱复配,所述椰油基羟乙基磺酸钠、月桂基葡萄糖羧酸钠和椰油酰胺基丙基甜菜碱的重量比为1:0.7:5;
所述可降解膜的制备方法,包括以下步骤:将高密度聚乙烯、低密度聚乙烯、聚乳酸、聚乙交酯、棉秆细粉、变性淀粉、分散剂、增塑剂和表面活性剂混合均匀得混合物料;然后将混合物料放入双螺杆挤出机中熔融共混后145℃挤出,即得所述可降解膜。
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