CN108602597A - 可生物降解的聚合物片材 - Google Patents

可生物降解的聚合物片材 Download PDF

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CN108602597A
CN108602597A CN201680078970.0A CN201680078970A CN108602597A CN 108602597 A CN108602597 A CN 108602597A CN 201680078970 A CN201680078970 A CN 201680078970A CN 108602597 A CN108602597 A CN 108602597A
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sheet material
polymer sheet
layer
biodegradable polymer
material according
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什洛莫·阿尔卡赫
丹·莱维特斯
阿莫斯·奥菲
阿纳·里·多坦
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Elbit Systems Ltd
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Elbit Systems Ltd
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Abstract

本发明的方面涉及可生物降解的聚合物片材，其包括:第一层和第二层，所述第一层包括以至多50％的重量％、例如至多25重量％的多糖以及聚合物基质，所述第一层被构造成在与水接触时形成防水层，所述第二层包括以至少40％的重量％的多糖以及聚合物基质。所述可生物降解的聚合物片材还包括第三层，所述第三层包括以至多50％的重量％、例如至多25重量％的多糖以及聚合物基质，所述第三层被构造成在与水接触时形成防水层。所述可生物降解的聚合物片材响应于暴露至自由空气和自然日光，在地面上经历生物降解。

Description

可生物降解的聚合物片材
发明背景
存在对由可生物降解的材料制成的包装或塑料片材的不断增长的需求。需要被制造为可生物降解的聚合物包装或塑料片材与处置方法相符。一些已知的处置方法是：聚合物材料的解体(disintegration)和制成堆肥，将用过的包装或塑料片材掩埋在地下或用土壤覆盖它们。
解体涉及由聚合物暴露至UV光(例如来自太阳的UV光)导致的在聚合物链之间的键中的至少一些的断裂，由此导致聚合物包装解体成小片。这样的小片如果不进一步分解，可能会在垃圾场或容器中余留多年。制成堆肥或地下掩埋涉及聚合物完全裂解成二氧化碳、水、无机化合物和生物质，没有留下可辨识的或有毒的残留物。
制成堆肥的过程是在密闭容器中、在具有受控的温度和湿度水平的受控环境下进行的，而地下掩埋需要使用重型机械来覆盖塑料残留物。制成堆肥的过程或地下降解过程涉及聚合物被微生物消化成有害化合物。这样的聚合物通常含有大量可消化的物质，例如作为微生物的“底物”的淀粉。
聚合物包装或聚合物片材在户外、在地面上完全解体并裂解成二氧化碳、水和其他有害化合物是非常合意的。此外，当意外地或有意地被燃烧时，聚合物包装的燃烧产物将不含有任何有害气体是合意的。
发明概述
本发明的一些实施方案可以涉及可生物降解的聚合物片材。这种可生物降解的聚合物片材可被构造成响应于暴露至自由空气和自然日光，在地面上经历生物降解。该可生物降解的聚合物片材可以包括第一层和第二层，第一层可以被构造成当与水接触时形成防水层(water barrier)，并且第二层包括富含多糖的共混物。本发明的一些实施方案可以是由前述可生物降解的聚合物片材制成的用于保存液体的容器的形式。
附图简述
被视为本发明的主题被特别地指出并且在本说明书的结论部分中被明确地要求保护。然而，当与附图一起阅读时，通过参考以下详细描述，本发明(关于组织和操作方法两者)连同其目的、特征、和优点可以被最好地理解，在附图中：
图1是根据本发明的一些实施方案的示例性的可生物降解的聚合物片材中的各个层的图示；和
图2是根据本发明的一些实施方案的示例性容器的图示。
将理解的是，为了简单且清楚阐明，在附图中示出的元件不一定按比例绘制。例如，为了清楚，元件中的某些的尺寸可以相对于其他元件被放大。此外，在认为合适的情况下，参考数字可以在附图中被重复以指示相应的或类似的元件。
本发明的详细描述
在以下详细描述中，大量具体的细节被陈述以便提供本发明的完全的理解。然而，本领域技术人员将理解本发明可以在没有这些具体细节的情况下被实践。在其他情况下，熟知的方法、程序和组分未被详细地描述，以免使本发明模糊。
本发明的一些方面可以涉及可生物降解的聚合物片材。这样的片材可用于形成用于保存液体如水或其它水溶液的包装和容器。如此处使用的，生物降解被定义为聚合物降解成CO2、水和生物质。在一些实施方案中，生物降解还可包含少量的无机物质(例如铁、碳酸钙)。根据本发明的实施方案的可生物降解的聚合物片材可以包括富含多糖的共混物，例如淀粉、纤维素、木质素和甲壳质。富含多糖的共混物是高度亲水的，因此，将这种化合物包括在用来形成用于水溶液的容器的聚合物片材中可能会增加困难。
在一些实施方案中，响应于暴露至自由空气和自然日光，可生物降解的聚合物片材可能必须在地面上(例如，在地表上、在土壤上)经历生物降解。当在自由空气中留在地面上时，根据本发明的实施方案的可生物降解的聚合物片材或者由这种聚合物片材制成的容器可分解成CO2、水和生物质。生物降解可以通过在地面上由微生物(例如细菌)、真菌或其他生物体消化和/或消耗聚合物片材来引起。生物降解过程可能花费相对短的时间段，例如6个月、12个月、18个月或24个月。
在一些实施方案中，为了加速生物降解，聚合物片材还可构造成被解体成小的聚合物片。来自太阳(在白天里)的紫外光可以引起聚合物链的降解。此过程可以通过向聚合物添加促氧化添加剂(pro-oxidative additive)来加速。
因此，根据本发明的一些实施方案的可生物降解的聚合物片材可以包括两层或更多层。第一层可以被构造为充当用于保存水或水溶液的有效防水层，并且第二层被构造为促进整个聚合物片材的生物降解。
现在参考图1，图1是根据本发明的一些实施方案的示例性的可生物降解的聚合物片材中的各个层的图示。可生物降解的聚合物片材100可以包括第一层110和第二层120，第一层110和第二层120包括富含多糖的共混物。第一层110可以被构造成当与水接触时形成防水层，防水层可维持至少一周。可生物降解的聚合物片材100可响应于暴露至自由空气和自然日光而在地面上经历生物降解。可生物降解的聚合物片材100可以使用任何已知的制造多层聚合物片材的方法来制造。可生物降解的聚合物片材100可具有至少30μm、40μm或50μm或更大的总厚度。在一些实施方案中，聚合物片材100的总厚度可以是至多100μm、150μm、200μm、300μm、500μm或1mm。
在一些实施方案中，第一层110可以包括聚合物基质和填料。聚合物基质可以包括例如聚酯、聚乙烯或类似物，并且填料可以包括富含多糖的共混物，例如淀粉、纤维素、木质素、甲壳质或其任何组合。在一些实施方案中，第一层可以包括至多25重量％的多糖。在一些实施方案中，第一层可以包括至多50重量％的多糖，例如至多40重量％。在一些实施方案中，第一层110可以具有至少5μm，例如10μm、20μm、30μm的厚度。
在一些实施方案中，第一层还可以包括添加剂，该添加剂被构造成当暴露至自然日光时加速聚合物片材的解体。这样的添加剂可以包括促氧化添加剂(也称为OXO添加剂)。示例性的OXO添加剂可以包括已知在低浓度(例如5000PPM和更低)诱导聚烯烃中的裂解和降解的过渡金属硬脂酸盐。过渡金属可以在两种氧化态之间转换，导致催化分解为氢过氧化物，氢过氧化物加速降解过程。
在一些实施方案中，第一层可以被构造成阻止水分子迁移持续至少3小时、6小时、1/2天、一天、2天、5天、一周或更长。例如，当包括第一层110的片材100的第一侧与水接触时，第一层110可以被构造成允许在至少3小时、6小时、1/2天、一天、2天、5天、一周或更长的期间内，不超过10％的水从片材100的第一侧扩散到片材100的第二侧。在一些实施方案中，片材100可以与水完全接触，使得层110的每个外部部分可以与水接触。在一些实施方案中，水还可以将压力施加在聚合物片材100上，并且层110可以在所施加的压力下保持防水层，如下面关于图2所公开的。在一些实施方案中，根据ASTM E-96标准，可生物降解的聚合物片材100在37℃的整体水蒸气传输速率(entire water vapor transmission rate)可以不超过50-800[g/m2天]。由聚合物片材100制成的示例性容器(例如牛奶袋)可以保存水或其他水基溶液持续至少一周，即使当多个容器(例如填充有水基溶液的袋)被一起保持在罐中时，使得罐中的上部容器可以挤压下部容器。示例性的容器在图2中被图示。
示例性的第一层110可以包括具有20-40重量％热塑性淀粉和0.5重量％C54H105FeO6(FeSt OXO)的聚酯。这样的组合物可以形成具有良好的冲击性质和强度性质的防水层。然而，由于相对低的淀粉含量，这样的层可能仅具有中等的可生物降解性。
第二层120可以包括聚合物基质和填料。填料可以包括富含多糖的共混物，例如为层120的总重量的至少40重量％。富含多糖的共混物可以是淀粉、纤维素、木质素、甲壳质或其组合。基质可以包括聚合物，例如聚酯、聚乙烯或类似物。第二层120可以被构造成通过为细菌、真菌或其他微生物提供更多营养物质用于消耗来增强片材100的生物降解。层120中的富含多糖的共混物可以供应营养物质。在一些实施方案中，第一层120可以具有至少20μm，例如40μm、60μm或更大的厚度。
在一些实施方案中，第二层120还可以包括添加剂，该添加剂被构造成当暴露至自然日光时加速聚合物片材的解体。如本文所讨论，这样的添加剂可以包括促氧化添加剂(也称为OXO添加剂)。
在一些实施方案中，添加大量的富含多糖的共混物可以降低层的机械强度，并且还可以使层高度亲水。因此，尽管具有非常好的生物降解性质，但是第二层120不可以独自地形成用于保存水基溶液的容器。
在一些实施方案中，可生物降解的片材100还可以包括第三层130。层130可以位于层120的另一侧，不附接到层110(如所图示的)，使得第二层120被层110和层130从两侧覆盖。层130可以被构造成当与水接触时形成防水层。防水层可以持续至少3小时、6小时、1/2天、一天、2天、5天、一周或更长。层130可以包括聚合物基质和填料。聚合物基质可以包括例如聚酯、聚乙烯或类似物，并且填料可以包括富含多糖的共混物，例如淀粉、纤维素、木质素、甲壳质或其任何组合。在一些实施方案中，第一层可以包括至多25重量％的富含多糖的共混物。在一些实施方案中，第一层可以包括至多25重量％的多糖。在一些实施方案中，第三层可以包括至多50重量％的多糖，例如至多40重量％。在一些实施方案中，第一层130可以具有至少5μm，例如20μm的厚度。
第三层130可以被构造成阻止水分子穿过聚合物片材100。例如，当片材100被包括在用于保存水的容器中时，第三层130可以允许少于10％的保存在容器中的水在一周的期间内从容器中蒸发。片材100的三层结构可以被构造成防止水和湿气与亲水层120接触。在一些实施方案中，片材100可以包括多于三层。
在一些实施方案中，可生物降解的片材100可以具有至少10MPa，例如15MPa、20MPa、30MPa或更高的拉伸强度。在一些实施方案中，可生物降解的片材100可以具有至少100％、200％、300％、400％或更高的断裂伸长率。在一些实施方案中，第一层110除了是防水层之外，还可以提供其中将使用聚合物片100的各种应用所需的拉伸强度。例如，将水保存在由片材100制成的容器中所需的强度。
在一些实施方案中，层110越厚，片材100可能越坚固。与具有比第二层120薄或具有相同厚度的第一层110的片材相比，具有比第二层120厚的第一层110的片材100可以具有更高的拉伸强度。例如，对于相同总厚度(例如100μm)，包括60％层110(例如60μm)和40％(例如40μm)层120的层厚比的片材100可以比具有50％(例如50μm)的每一层的片材100更坚固。当添加另外的第三层例如具有与层110相似或接近的性质的层130时，强度还可以增加。因此，(对于相同的总厚度)具有以下厚度比：30％层110、40％层120和30％层130的三层片材可以具有比具有以下厚度比：25％层110、50％层120和25％层130的三层片材更高的拉伸强度。在一些实施方案中，片材100的总厚度以及第一层、第二层和任选的第三层之间的厚度比可以根据最终所需的拉伸强度来确定。例如，水(或其他液体)容器例如图2的容器所需的拉伸强度。
现在参考图2，图2是根据本发明的一些实施方案的用于保存水基溶液的容器200的图示。容器200可以由可生物降解的片材100制造。容器200可以包括密封件(sealing)210。密封件210可以是足够牢固的以将水保存在容器200内而没有断裂或水蒸发。容器200可以被密封成使得在一天、2天、5天、一周或更长的期间内不超过10重量％的保存在容器中的水可以蒸发。容器200可以具有各种尺寸，每种尺寸被设计成保存不同量的液体。容器200可以被设计成保存从1毫升(ml)-100升(l)或更多的液体。例如，10ml、50ml、100ml、200ml、500ml、1升、5升和10升。
在一些实施方案中，容器200的强度可以是使得当多个容器200堆叠在一起时，例如在罐中，片材100和密封件210两者均可以将水保存在多个容器200中的每一个内。例如，片材100和密封件210的强度可以是使得装满水的具有200ml的体积的容器200可以耐受由至少30kg、40kg、50kg或更多的外部负载施加在装满的容器上的压缩压力。
在一些实施方案中，可生物降解的聚合物片材100和容器200可以被构造成响应于暴露至自由空气和自然日光，在不超过24个月的期间内，例如在不超过18个月的期间内，在不超过12个月的期间内或在不超过6个月的期间内，在地面上经历生物降解。可生物降解的聚合物片材100和容器200可以根据以下中的至少一种经历生物降解至环境无害的物质:ISO 20200、ASTM 6400、ISO 14855和EN 13432。例如，在自由空气中留在地面上的片材100和容器200可以通过位于土壤中的细菌和/或真菌经历生物降解，以产生CO2、水和生物质。
在一些实施方案中，当放置在火中(故意地或无意地)时，片材100和容器200可以被构造成在火中燃烧而不排放危险气体。如本文所使用的，危险气体可以包括在大量吸入或摄取时对人类有害的气体。另外，危险气体还可以包括可以继续燃烧或可能爆炸的气体。例如，不完全燃烧可能导致有毒的CO的排放，在层110、层120或层130的至少一个中向聚合物基质中添加各种化学品可能导致排放其他有害气体。因此，片材100和容器200可以仅包括能够完全燃烧以形成CO2(在户外)且不排放任何其他有毒或危险气体的材料。
实验结果
使用具有如表1中列出的结构和组成的可生物降解的聚合物片材来进行实验:
表1：
拉伸试验
对具有表1中公开的结构的可生物降解的聚合物片材进行拉伸试验。将可生物降解的聚合物片材在两个方向:机器方向(MD-挤压方向)和横向方向(TD)上测试7次。在最大负载处的平均应力和在断裂点处的应变在表2中给出:试验以23℃的温度、50％的湿度、0.5kN的满负载和500mm/min的十字头速度(crosshead speed)进行。
表2.
如可以清楚地看到的，两个方向上的最大负载处的平均应力都高于10MPa，并且断裂点处的应变或伸长率远高于100％。
地面上的生物降解试验
测试具有表1中公开的结构的可生物降解的聚合物片材的响应于暴露至自由空气和自然日光在地面上的生物降解。图3A和3B是在加利福尼亚的夏季期间留在地面上之后，在第1天(图3A)和第63天(图3B)拍摄的3种类型的片材310-330的照片。片材310由纸制成，片材320由上文公开的相同的可生物降解的聚合物片材制成，且片材330在河水中浸泡1小时后是与片材320相同的片材。如可以清楚地看出的，在63天后，所有的可生物降解的聚合物片材都解体并至少部分地降解，而纸片保持不变。如所预期的，当添加甚至少量的水时，片材的可生物降解性增加。
水传输试验
测试具有表1中公开的结构的可生物降解的聚合物片材的两个样品的水蒸气传输。两个样品的水蒸气传输是376g/(m2·天)和327g/(m2·天)。两个样品的水蒸气传输均小于380g/(m2·天)。
尽管本文已经阐明和描述了本发明的某些特征，但是本领域普通技术人员现在将想到许多修改、替换、改变和等同物。因此，将理解的是，所附权利要求意图覆盖落在本发明的真实精神范围内的所有这样的修改和变化。

Claims (22)

1.一种可生物降解的聚合物片材，包括:
第一层，所述第一层包括以至多25％的重量％的多糖以及聚合物基质，所述第一层被构造成当与水接触时形成防水层；
第二层，所述第二层包括以至少40％的重量％的多糖以及聚合物基质；和
第三层，所述第三层包括以至多25％的重量％的多糖以及聚合物基质，所述第三层被构造成当与水接触时形成防水层，
其中所述可生物降解的聚合物片材响应于暴露至自由空气和自然日光，在地面上经历生物降解。
2.根据权利要求1所述的可生物降解的聚合物片材，其中所述生物降解在不超过18个月的期间内发生。
3.根据权利要求1所述的可生物降解的聚合物片材，其中所述生物降解在不超过6个月的期间内发生。
4.根据权利要求1或2所述的可生物降解的聚合物片材，还包括添加剂，所述添加剂被构造成当暴露至自然日光时加速所述聚合物片材的解体。
5.根据前述权利要求中任一项所述的可生物降解的聚合物片材，其中所述多糖包括以下中的至少一种：淀粉、纤维素、木质素和甲壳质。
6.根据前述权利要求中任一项所述的可生物降解的聚合物片材，其中，根据ASTM E-96，所述可生物降解的聚合物片材在37℃的水蒸气传输速率在50-800[g/m2天]之间。
7.根据前述权利要求中任一项所述的可生物降解的聚合物片材，具有至少10MPa的拉伸强度。
8.根据前述权利要求中任一项所述的可生物降解的聚合物片材，具有至少100％的断裂伸长率。
9.根据前述权利要求中任一项所述的可生物降解的聚合物片材，还被构造成根据以下中的至少一种经历完全生物降解至环境无害的材料:ISO20200、ASTM 6400、ISO 14855和EN13432。
10.根据前述权利要求中任一项所述的可生物降解的聚合物片材，还被构造成在火中燃烧而不排放危险气体。
11.一种用于保存液体的容器，所述容器由根据前述权利要求中任一项所述的可生物降解的聚合物片材制成。
12.一种可生物降解的聚合物片材，包括:
第一层，所述第一层包括以至多50％的重量％的多糖以及聚合物基质，所述第一层被构造成当与水接触时形成防水层；
第二层，所述第二层包括以至少50％的重量％的多糖以及聚合物基质；和
第三层，所述第三层包括以至多40％的重量％的多糖以及聚合物基质，所述第三层被构造成当与水接触时形成防水层，
其中所述可生物降解的聚合物片材响应于暴露至自由空气和自然日光，在地面上经历生物降解。
13.根据权利要求13所述的可生物降解的聚合物片材，其中所述生物降解在不超过18个月的期间内发生。
14.根据权利要求13所述的可生物降解的聚合物片材，其中所述生物降解在不超过6个月的期间内发生。
15.根据权利要求12或14所述的可生物降解的聚合物片材，还包括添加剂，所述添加剂被构造成当暴露至自然日光时加速所述聚合物片材的解体。
16.根据权利要求12-15中任一项所述的可生物降解的聚合物片材，其中所述多糖包括以下中的至少一种：淀粉、纤维素、木质素和甲壳质。
17.根据权利要求12-16中任一项所述的可生物降解的聚合物片材，其中，根据ASTM E-96，所述可生物降解的聚合物片材在37℃的水蒸气传输速率在50-800[g/m2天]之间。
18.根据权利要求12-17中任一项所述的可生物降解的聚合物片材，具有至少10MPa的拉伸强度。
19.根据权利要求12-18中任一项所述的可生物降解的聚合物片材，具有至少100％的断裂伸长率。
20.根据权利要求12-19中任一项所述的可生物降解的聚合物片材，还被构造成根据以下中的至少一种经历完全生物降解至环境无害的材料:ISO 20200、ASTM 6400、ISO 14855和EN 13432。
21.根据权利要求12-20中任一项所述的可生物降解的聚合物片材，还被构造成在火中燃烧而不排放危险气体。
22.一种用于保存液体的容器，所述容器由根据权利要求12-21中任一项所述的可生物降解的聚合物片材制成。
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