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穿针引线:用丁二烯衍生的聚烯烃嵌段共聚物使高密度聚乙烯/聚丙烯共混物相容化

Threading-the-Needle: Compatibilization of HDPE/PP blends with butadiene-derived polyolefin block copolymers.

作者信息

Shen Liyang, Gorbea Gabriela Diaz, Danielson Evan, Cui Shuquan, Ellison Christopher J, Bates Frank S

机构信息

Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN 55455.

Department of Chemistry, University of Minnesota, Minneapolis, MN 55455.

出版信息

Proc Natl Acad Sci U S A. 2023 Aug 22;120(34):e2301352120. doi: 10.1073/pnas.2301352120. Epub 2023 Aug 14.

Abstract

Management of the plastic industry is a momentous challenge, one that pits enormous societal benefits against an accumulating reservoir of nearly indestructible waste. A promising strategy for recycling polyethylene (PE) and isotactic polypropylene (PP), constituting roughly half the plastic produced annually worldwide, is melt blending for reformulation into useful products. Unfortunately, such blends are generally brittle and useless due to phase separation and mechanically weak domain interfaces. Recent studies have shown that addition of small amounts of semicrystalline PE-PP block copolymers (ca. 1 wt%) to mixtures of these polyolefins results in ductility comparable to the pure materials. However, current methods for producing such additives rely on expensive reagents, prohibitively impacting the cost of recycling these inexpensive commodity plastics. Here, we describe an alternative strategy that exploits anionic polymerization of butadiene into block copolymers, with subsequent catalytic hydrogenation, yielding E and X blocks that are individually melt miscible with PE and PP, where E and X are poly(ethylene--ethylethylene) random copolymers with 6 wt% and 90 wt% ethylethylene repeat units, respectively. Cooling melt blended mixtures of PE and PP containing 1 wt% of the triblock copolymer EXE of appropriate molecular weight, results in mechanical properties competitive with the component plastics. Blend toughness is obtained through interfacial topological entanglements of the amorphous X polymer and semicrystalline PP, along with anchoring of the E blocks through cocrystallization with the PE homopolymer. Significantly, EXE can be inexpensively produced using currently practiced industrial scale polymerization methods, offering a practical approach to recycling the world's top two plastics.

摘要

塑料行业的管理是一项重大挑战,它使巨大的社会效益与不断累积的几乎不可降解的废物库形成了鲜明对比。聚乙烯(PE)和全同立构聚丙烯(PP)约占全球每年塑料产量的一半,一种很有前景的回收策略是将它们熔融共混,重新制成有用的产品。不幸的是,由于相分离和机械性能较弱的畴界面,这种共混物通常很脆,没有用处。最近的研究表明,向这些聚烯烃的混合物中添加少量半结晶的PE-PP嵌段共聚物(约1 wt%),可使其延展性与纯材料相当。然而,目前生产此类添加剂的方法依赖于昂贵的试剂,这对回收这些廉价的通用塑料的成本产生了过高的影响。在此,我们描述了一种替代策略,该策略利用丁二烯的阴离子聚合反应生成嵌段共聚物,随后进行催化氢化,生成E段和X段,它们分别与PE和PP熔融互溶,其中E和X分别是具有6 wt%和90 wt%乙基乙烯重复单元的聚(乙烯-乙基乙烯)无规共聚物。冷却含有1 wt%适当分子量的三嵌段共聚物EXE的PE和PP的熔融共混物,可得到与组成塑料具有竞争力的机械性能。共混物的韧性是通过无定形X聚合物与半结晶PP的界面拓扑缠结,以及E段通过与PE均聚物共结晶而实现的。值得注意的是,EXE可以使用目前的工业规模聚合方法廉价地生产,为回收全球排名前两位的塑料提供了一种切实可行(的方法)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5cae/10450653/24d8e14e1a21/pnas.2301352120fig01.jpg

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