Darin Sukalingum, Tianran Zhai, Marc H. Weber, Sohraab A. Khan, Thant H. Htut, Jeremy I. Feldblyum
{"title":"Pore Network Percolation in Polymers of Intrinsic Microporosity Examined by Gaseous and Antimatter Probes","authors":"Darin Sukalingum, Tianran Zhai, Marc H. Weber, Sohraab A. Khan, Thant H. Htut, Jeremy I. Feldblyum","doi":"10.1021/acs.macromol.5c00945","DOIUrl":null,"url":null,"abstract":"Synthesis of polymers with tailored properties requires an understanding of the underlying phenomena leading to these properties. Polymers of intrinsic microporosity (PIMs) are non-network polymers with a substantial guest-accessible free volume. Their BET surface areas have been reported to be as high as 1000 m<sup>2</sup>/g, and their porosity has led to the demonstration of some of the best membrane-based gas separations to date. However, it has been challenging to predict porosity in PIMs a priori, in part due to an incomplete framework for understanding the origins of porosity in these materials. Here, porosity in several archetypal PIMs is examined through the lens of a percolation model, whereby porosity in oligomers follows behavior expected for nonpercolated and percolated networks. Positron-based Doppler broadening spectroscopy is used to examine buried pores in samples whose pores are inaccessible to typical (nonantimatter) guests and demonstrate that buried pores are present in PIMs with nonpercolated pore networks. Taken together, the findings are in agreement with the contention that network percolation plays a critical role in pore accessibility in PIMs.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"121 1","pages":""},"PeriodicalIF":5.2000,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.5c00945","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
Abstract
Synthesis of polymers with tailored properties requires an understanding of the underlying phenomena leading to these properties. Polymers of intrinsic microporosity (PIMs) are non-network polymers with a substantial guest-accessible free volume. Their BET surface areas have been reported to be as high as 1000 m2/g, and their porosity has led to the demonstration of some of the best membrane-based gas separations to date. However, it has been challenging to predict porosity in PIMs a priori, in part due to an incomplete framework for understanding the origins of porosity in these materials. Here, porosity in several archetypal PIMs is examined through the lens of a percolation model, whereby porosity in oligomers follows behavior expected for nonpercolated and percolated networks. Positron-based Doppler broadening spectroscopy is used to examine buried pores in samples whose pores are inaccessible to typical (nonantimatter) guests and demonstrate that buried pores are present in PIMs with nonpercolated pore networks. Taken together, the findings are in agreement with the contention that network percolation plays a critical role in pore accessibility in PIMs.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.