Host-guest co-amorphous structure revealed by the suppression of the first sharp diffraction peak in isotactic poly(4-methyl-1-pentene)

TL;DR

This study uncovers a novel host-guest co-amorphous structure in a semicrystalline polymer, where guest molecules occupy internal voids, demonstrated by suppression of the first sharp diffraction peak in X-ray diffraction patterns.

Contribution

It provides the first experimental evidence of a host-guest co-amorphous system at room temperature, revealing new insights into amorphous materials with guest molecule incorporation.

Findings

Suppression of the FSDP in P4MP1 when immersed in decane.

Isolation of amorphous FSDP using stretched samples.

Identification of a host-guest co-amorphous structure at ambient conditions.

Abstract

While host-guest co-crystals are well established, and co-amorphous solids are recognized in materials science, the concept of a host-guest co-amorphous structure remains largely unexplored. A potential analogue is seen in SiO2 glass under high pressure with helium as a pressure medium; the drop in compressibility in this system is ascribed to helium atoms occupying internal voids. In this study, we investigated a semicrystalline polymer, isotactic poly(4-methyl-pentene-1) (P4MP1), which shares key characteristics with SiO2 glass, particularly regarding the first sharp diffraction peak (FSDP). The FSDP in P4MP1 is attributed to internal voids, as evidenced by its suppression under pressure and recovery upon decompression for molten P4MP1. Notably, the response to helium as a pressure medium is also known to parallel the behavior observed in SiO2 glass. Here, we analyzed two-dimensional X-ray diffraction (2D-XRD) patterns of stretched P4MP1 and found a suppression of FSDP when P4MP1 is immersed in decane. The use of stretched samples enabled the clear isolation of the amorphous FSDP from overlapping crystalline diffractions. Our findings reveal the existence of a host-guest co-amorphous system at room temperature and atmospheric pressure, in which decane molecules occupy the amorphous host matrix of P4MP1. Unlike conventional co-amorphous mixtures, this structure is defined by the specific accommodation of guests within the host's inherent voids. Intriguingly, the signature of this structure in diffraction measurements, manifested as changes in the FSDP intensity ratio, may be regarded to parallel the variations in Bragg peak intensity ratios in host-guest co-crystals. Since selective sorption and guest exchange are well-known in co-crystals, hosts capable of forming co-amorphous structures will be promising materials for molecular sieves, or more generally, liquid-phase molecular sieves.