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交联扩链剂对堆肥 PBAT/PLA 吹塑薄膜崩解行为的影响。

Effect of Chain Extending Cross-Linkers on the Disintegration Behavior of Composted PBAT/PLA Blown Films.

机构信息

Faculty of Technology, Tomas Bata University in Zlín, Vavreckova 275, 76001 Zlín, Czech Republic.

Department of Natural Sciences, University of Applied Sciences Bonn-Rhein-Sieg, von Liebig Str. 20, 53359 Rheinbach, Germany.

出版信息

Int J Mol Sci. 2023 Feb 24;24(5):4525. doi: 10.3390/ijms24054525.

Abstract

A biodegradable blend of PBAT-poly(butylene adipate-co-terephthalate)-and PLA-poly(lactic acid)-for blown film extrusion was modified with four multi-functional chain extending cross-linkers (CECL). The anisotropic morphology introduced during film blowing affects the degradation processes. Given that two CECL increased the melt flow rate (MFR) of tris(2,4-di-tert-butylphenyl)phosphite (V1) and 1,3-phenylenebisoxazoline (V2) and the other two reduced it (aromatic polycarbodiimide (V3) and poly(4,4-dicyclohexylmethanecarbodiimide) (V4)), their compost (bio-)disintegration behavior was investigated. It was significantly altered with respect to the unmodified reference blend (REF). The disintegration behavior at 30 and 60 °C was investigated by determining changes in mass, Young's moduli, tensile strengths, elongations at break and thermal properties. In order to quantify the disintegration behavior, the hole areas of blown films were evaluated after compost storage at 60 °C to calculate the kinetics of the time dependent degrees of disintegration. The kinetic model of disintegration provides two parameters: initiation time and disintegration time. They quantify the effects of the CECL on the disintegration behavior of the PBAT/PLA compound. Differential scanning calorimetry (DSC) revealed a pronounced annealing effect during storage in compost at 30 °C, as well as the occurrence of an additional step-like increase in the heat flow at 75 °C after storage at 60 °C. The disintegration consists of processes which affect amorphous and crystalline phase of PBAT in different manner that cannot be understood by a hydrolytic chain degradation only. Furthermore, gel permeation chromatography (GPC) revealed molecular degradation only at 60 °C for the REF and V1 after 7 days of compost storage. The observed losses of mass and cross-sectional area seem to be attributed more to mechanical decay than to molecular degradation for the given compost storage times.

摘要

用于吹塑薄膜挤出的 PBAT-聚(丁二酸丁二醇酯-对苯二甲酸酯)和 PLA-聚(乳酸)可生物降解共混物用四种多功能链扩展交联剂(CECL)进行了改性。在吹膜过程中引入的各向异性形态会影响降解过程。由于两种 CECL 增加了三(2,4-二叔丁基苯基)亚磷酸酯(V1)和 1,3-亚苯基双恶唑啉(V2)的熔体流动速率(MFR),而另外两种则降低了熔体流动速率(芳族聚碳化二亚胺(V3)和聚(4,4-二环己基甲烷碳化二亚胺)(V4)),因此研究了它们的共混物(生物)分解行为。与未改性的参考共混物(REF)相比,其分解行为发生了显著变化。通过测定质量、杨氏模量、拉伸强度、断裂伸长率和热性能的变化,研究了 30 和 60°C 下的分解行为。为了量化分解行为,在 60°C 下进行堆肥储存后,评估吹塑薄膜的孔面积,以计算时间相关分解度的动力学。分解动力学模型提供了两个参数:起始时间和分解时间。它们量化了 CECL 对 PBAT/PLA 化合物分解行为的影响。差示扫描量热法(DSC)显示,在 30°C 下在堆肥中储存时会产生明显的退火效应,以及在 60°C 下储存后在 75°C 时会发生额外的阶跃式热流增加。分解过程包括不能仅通过水解链降解来理解的影响 PBAT 无定形和结晶相的不同方式的过程。此外,凝胶渗透色谱(GPC)仅在 REF 和 V1 在堆肥储存 7 天后于 60°C 下显示分子降解。对于给定的堆肥储存时间,观察到的质量和截面积损失似乎更多归因于机械降解而不是分子降解。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4614/10003261/25ba7b5eb244/ijms-24-04525-g001.jpg

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