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Polymers
Special Issues
Characterization and Application of Block Copolymers
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Characterization and Application of Block Copolymers

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (10 March 2024) | Viewed by 8614

Special Issue Editors

Dr. Aparna Beena Unni

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Guest Editor
Institute of Physics, Uniwersytet Slaski w Katowicach, Katowice, Poland
Interests: polymer nanocomposites; polymer thin films; confinement; vapor deposited glasses
Prof. Dr. June Huh

E-Mail Website
Guest Editor
Department of Chemical and Biological Engineering, Korea University, Seoul, Republic of Korea
Interests: soft matter theory and simulation; block copolymers; polymer blends; bottlebrush polymer; polymer degradation; biodegradable polymers

Special Issue Information

Dear Colleagues,

This Special Issue will deal with the synthesis, characterization, and application of a special class of materials, namely, block copolymers. They are generally formed by grouping chemically distinct monomer units as distinct blocks along a polymer chain. This specific class of copolymers is found to have many interdisciplinary technological applications. This Issue specifically focuses on novel experimental techniques/methods for the synthesis and characterization of novel/hybrid co-polymeric materials. The practical technological applications of block copolymers in various areas, such as chemistry, materials sciences, medicinal and biological applications, etc., will also be contemplated. Full research articles, short communications, and review articles on the topic will be considered.

Dr. Aparna Beena Unni
Prof. Dr. June Huh
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • block copolymers
  • synthesis of block copolymers
  • applications of block copolymers
  • characterization of block copolymers
  • self-assembly

Published Papers (5 papers)

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Research

25 pages, 4573 KiB  
Article
Synthesis and Characterization of ABA-Type Triblock Copolymers Using Novel Bifunctional PS, PMMA, and PCL Macroinitiators Bearing p-xylene-bis(2-mercaptoethyloxy) Core
by Murat Mısır, Sevil Savaskan Yılmaz and Ahmet Bilgin
Polymers 2023, 15(18), 3813; https://doi.org/10.3390/polym15183813 - 18 Sep 2023
Cited by 2 | Viewed by 1248
Abstract
Syntheses of novel bifunctional poly(methyl methacrylate) (PMMA)-, poly(styrene) (PS)-, and (poly ε-caprolactone) (PCL)-based atom transfer radical polymerization (ATRP) macroinitiators derived from p-xylene-bis(1-hydroxy-3-thia-propanoloxy) core were carried out to obtain ABA-type block copolymers. Firstly, a novel bifunctional ATRP initiator, 1,4-phenylenebis(methylene-thioethane-2,1-diyl)bis(2-bromo-2-methylpropanoat) (PXTBR), synthesized the [...] Read more.
Syntheses of novel bifunctional poly(methyl methacrylate) (PMMA)-, poly(styrene) (PS)-, and (poly ε-caprolactone) (PCL)-based atom transfer radical polymerization (ATRP) macroinitiators derived from p-xylene-bis(1-hydroxy-3-thia-propanoloxy) core were carried out to obtain ABA-type block copolymers. Firstly, a novel bifunctional ATRP initiator, 1,4-phenylenebis(methylene-thioethane-2,1-diyl)bis(2-bromo-2-methylpropanoat) (PXTBR), synthesized the reaction of p-xylene-bis(1-hydroxy-3-thia-propane) (PXTOH) with α-bromoisobutryl bromide. The PMMA and PS macroinitiators were prepared by ATRP of methyl methacrylate (MMA) and styrene (S) as monomers using (PXTBR) as the initiator and copper(I) bromide/N,N,N′,N″,N″-pentamethyldiethylenetriamine (CuBr/PMDETA) as a catalyst system. Secondly, di(α-bromoester) end-functionalized PCL–based ATRP macronitiator (PXTPCLBr) was prepared by esterification of hydroxyl end groups of PCL-diol (PXTPCLOH) synthesized by Sn(Oct)2–catalyzed ring opening polymerization (ROP) of ε-CL in bulk using (PXTOH) as initiator. Finally, ABA-type block copolymers, PXT(PS-b-PMMA-b-PS), PXT(PMMA-b-PS-b-PMMA), PXT(PS-b-PCL-b-PS), and PXT(PMMA-b-PCL-b-PMMA), were synthesized by ATRP of MMA and S as monomers using PMMA-, PS-, and PCL-based macroinitiators in the presence of CuBr/PMDETA as the catalyst system in toluene or N,N-dimethylformamide (DMF) at different temperatures. In addition, the extraction abilities of PCL and PS were investigated under liquid–liquid phase conditions using heavy metal picrates (Ag+, Cd2+, Cu2+, Hg2+, Pb2+, and Zn2+) as substrates and measuring with UV-Vis the amounts of picrate in the 1,2–dichloroethane phase before and after treatment with the polymers. The extraction affinity of PXTPCL and PXTPS for Hg2+ was found to be highest in the liquid–liquid phase extraction experiments. Characterizations of the molecular structures for synthesized novel initiators, macroinitiators, and the block copolymers were made by spectroscopic (FT–IR, ESI–MS, 1H NMR, 13C NMR), DSC, TGA, chromatographic (GPC), and morphologic SEM. Full article
(This article belongs to the Special Issue Characterization and Application of Block Copolymers)
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23 pages, 6191 KiB  
Article
The Effect of Functionalized SEBS on the Properties of PP/SEBS Blends
by Lixin Song, Fei Cong, Wei Wang, Jiannan Ren, Weihan Chi, Bing Yang, Qian Zhang, Yongchao Li, Xianliang Li and Yuanxia Wang
Polymers 2023, 15(18), 3696; https://doi.org/10.3390/polym15183696 - 08 Sep 2023
Cited by 2 | Viewed by 1866
Abstract
Styrene (St) was used as comonomer and glycidyl methacrylate (GMA) as grafting monomer to prepare SEBS-g-(GMA-co-St) graft copolymers via melt grafting. Then, the graft copolymers were employed as a compatibilizer for melt blending polypropylene (PP) and hydrogenated styrene-butadiene-styrene (SEBS) triblock copolymers. The effects [...] Read more.
Styrene (St) was used as comonomer and glycidyl methacrylate (GMA) as grafting monomer to prepare SEBS-g-(GMA-co-St) graft copolymers via melt grafting. Then, the graft copolymers were employed as a compatibilizer for melt blending polypropylene (PP) and hydrogenated styrene-butadiene-styrene (SEBS) triblock copolymers. The effects of the amount of GMA in the graft copolymers on thermal properties, rheology, crystallization, optical and mechanical properties, and microstructure of the blends were investigated. The results show that GMA and St were successfully grafted onto SEBS. The GMA amount in the graft copolymer significantly influenced the comprehensive properties of PP/SEBS/SEBS-g-(GMA-co-St) blends. The epoxy groups of GMA reacted with PP and SEBS, forming interfacial chemical bonds, thereby enhancing the compatibility between PP and SEBS to varying extents. After introducing SEBS-g-(GMA-co-St) into PP/SEBS blends, crystallinity decreased, crystal size increased while transmittance remained above 91% with rising GMA amount in the graft copolymers, indicating excellent optical properties. Notched impact strength and elongation at break of the blends showed a trend of first increasing and then decreasing with increased amounts of GMA in the graft copolymers. When the amount of GMA in the graft copolymers was 3 wt%, the blends exhibited optimal toughness with notched impact strength and elongation at break of 30,165.82 J/m2 and 1445.40%, respectively. This was attributed to the tightest dispersion interface adhesion and maximum matrix plastic deformation, consistent with the mechanical performance results. Full article
(This article belongs to the Special Issue Characterization and Application of Block Copolymers)
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17 pages, 5236 KiB  
Article
Effect of Octene Block Copolymer (OBC) and High-Density Polyethylene (HDPE) on Crystalline Morphology, Structure and Mechanical Properties of Octene Random Copolymer
by Yuan-Xia Wang, Cun-Ying Zou, Nan Bai, Qun-Feng Su, Li-Xin Song and Xian-Liang Li
Polymers 2023, 15(18), 3655; https://doi.org/10.3390/polym15183655 - 05 Sep 2023
Viewed by 959
Abstract
Blending octene random copolymer (ORC) with other polymers is a promising approach to improving ORC mechanical properties, such as tensile strength and elongation. In this study, octene block copolymer (OBC) with lower density than ORC and high-density polyethylene (HDPE) were used to blend [...] Read more.
Blending octene random copolymer (ORC) with other polymers is a promising approach to improving ORC mechanical properties, such as tensile strength and elongation. In this study, octene block copolymer (OBC) with lower density than ORC and high-density polyethylene (HDPE) were used to blend with ORC. The effect of both OBC and HDPE on ORC was analyzed using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and small-angle X-ray scattering (SAXS). For ORC/OBC blends, a small amount of OBC can improve the crystallization ability of ORC. Meanwhile, for ORC/HDPE blends, the crystallization ability of ORC was significantly suppressed, attributed to good compatibility between ORC and HDPE as indicated by the homogeneous morphology and the disappearance of the α transition peak of ORC in ORC/HDPE blends. Therefore, the tensile strength and elongation of ORC/HDPE blends are significantly higher than those of ORC/OBC blends. For ORC/OBC/HDPE ternary blends, we found that when ORC:OBC:HDPE are at a ratio of 70:15:15, cocrystallization is achieved. Although HDPE improves the compatibility of ORC and OBC, the three-phase structure of the ternary blends can be observed through SAXS when HDPE and OBC exceed 30 wt%. Blending HDPE and OBC (≤30 wt%) could improve the mechanical property of ORC. Full article
(This article belongs to the Special Issue Characterization and Application of Block Copolymers)
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12 pages, 1114 KiB  
Article
Effective Interaction between Homo- and Heteropolymer Block of Poly(n-butyl acrylate)-b-poly(methyl methacrylate-r-styrene) Diblock Copolymers
by Sang-In Lee, Min-Guk Seo, June Huh and Hyun-jong Paik
Polymers 2023, 15(13), 2915; https://doi.org/10.3390/polym15132915 - 30 Jun 2023
Viewed by 978
Abstract
We investigated the segregation behavior of a molten diblock copolymer, poly(n-butyl acrylate)-b-poly(methyl methacrylate-r-styrene) (PBA-b-P(MMA-r-S)), wherein styrene (S) is incorporated as a comonomer in the second block to modulate the effective interaction between homopolymer [...] Read more.
We investigated the segregation behavior of a molten diblock copolymer, poly(n-butyl acrylate)-b-poly(methyl methacrylate-r-styrene) (PBA-b-P(MMA-r-S)), wherein styrene (S) is incorporated as a comonomer in the second block to modulate the effective interaction between homopolymer and a random copolymer block. The temperature dependence of the effective interaction parameter χeff between n-butyl acrylate (BA) and the average monomer of the MMA-r-S random block was evaluated from small-angle X-ray scattering (SAXS) analysis using the random phase approximation (RPA) approach. The calculated χeff, as a function of the styrene fraction in the random copolymer block, shows a good agreement with the mean-field binary interaction model. This consistency indicates that the effective interaction between component BA and the average monomer of the random copolymer block is smaller than the interactions between pure components (χBA,MMA,χBA,S). The present study suggests that the introduction of a random copolymer block to a block copolymer can effectively reduce the degree of incompatibility of the block copolymer system without altering the constituent species, which may serve as a viable methodology in designing novel thermoplastic elastomers based on triblock or multiblock copolymers. Full article
(This article belongs to the Special Issue Characterization and Application of Block Copolymers)
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19 pages, 5463 KiB  
Article
Characterization of Polyisobutylene Succinic Anhydride (PIBSA) and Its PIBSI Products from the Reaction of PIBSA with Hexamethylene Diamine
by Franklin Frasca and Jean Duhamel
Polymers 2023, 15(10), 2350; https://doi.org/10.3390/polym15102350 - 17 May 2023
Cited by 1 | Viewed by 3010
Abstract
The nature of the end-groups of a PIBSA sample, namely a polyisobutylene (PIB) sample, where each chain is supposedly terminated at one end with a single succinic anhydride group, was characterized through a combination of pyrene excimer fluorescence (PEF), gel permeation chromatography, and [...] Read more.
The nature of the end-groups of a PIBSA sample, namely a polyisobutylene (PIB) sample, where each chain is supposedly terminated at one end with a single succinic anhydride group, was characterized through a combination of pyrene excimer fluorescence (PEF), gel permeation chromatography, and simulations. The PIBSA sample was reacted with different molar ratios of hexamethylene diamine to generate PIBSI molecules with succinimide (SI) groups in the corresponding reaction mixtures. The molecular weight distribution (MWD) of the different reaction mixtures was determined by fitting the gel permeation chromatography traces with sums of Gaussians. Comparison of the experimental MWD of the reaction mixtures with those simulated by assuming that the reaction between succinic anhydride and amine occurs through stochastic encounters led to the conclusion that 36 wt% of the PIBSA sample constituted unmaleated PIB chains. Based on this analysis, the PIBSA sample was found to be constituted of 0.50, 0.38, and 0.12 molar fractions of PIB chains that were singly maleated, unmaleated, and doubly maleated, respectively. Full article
(This article belongs to the Special Issue Characterization and Application of Block Copolymers)
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