{"title":"Density Functional Theory for Cyclic Block Copolymer Melts","authors":"Yoshinori Tomiyoshi, Takashi Honda, Toshihiro Kawakatsu, Takahiro Murashima, Erica Uehara, Tetsuo Deguchi","doi":"10.1021/acs.macromol.4c02003","DOIUrl":null,"url":null,"abstract":"We propose an efficient method for the self-assembly of Gaussian block copolymers with general cyclic architectures and nonconcatenated ring block copolymer in a melt based on a Ginzburg–Landau-type density functional theory combined with random phase approximation. For the Gaussian copolymers, the applicability of the density functional theory is enhanced by a Gaussian embedding method with a graph Laplacian, which allows evaluating single-chain scattering functions for arbitrary architectures including internal multicycles without analytical difficulty. By using this methodology, we predict phase diagrams of ring and bicycle diblock copolymers at the same cost as a linear diblock copolymer, and discover various metastable morphologies of a tadpole triblock terpolymer, which have not been observed for linear and star triblock terpolymers. We also demonstrate that our framework predicts the phase diagram of the nonconcatenated ring diblock copolymer with the aid of its single-chain scattering function obtained by experiments.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-11-05","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.4c02003","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
We propose an efficient method for the self-assembly of Gaussian block copolymers with general cyclic architectures and nonconcatenated ring block copolymer in a melt based on a Ginzburg–Landau-type density functional theory combined with random phase approximation. For the Gaussian copolymers, the applicability of the density functional theory is enhanced by a Gaussian embedding method with a graph Laplacian, which allows evaluating single-chain scattering functions for arbitrary architectures including internal multicycles without analytical difficulty. By using this methodology, we predict phase diagrams of ring and bicycle diblock copolymers at the same cost as a linear diblock copolymer, and discover various metastable morphologies of a tadpole triblock terpolymer, which have not been observed for linear and star triblock terpolymers. We also demonstrate that our framework predicts the phase diagram of the nonconcatenated ring diblock copolymer with the aid of its single-chain scattering function obtained by experiments.
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.