Special Issue "Synthesis, Characterization and Applications of Block Copolymers"

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Advanced Composites".

Deadline for manuscript submissions: closed (29 February 2020).

Special Issue Editor

Dr. Prokopios Georgopanos
Website
Guest Editor
Institute of Polymer Research, Helmholtz-Zentrum Geesthacht, Germany
Interests: anionic polymerization; block copolymers; complex architectures; polymer membranes; gas separation; liquid separation; polymer morphology; nanostructures; composite materials

Special Issue Information

Dear Colleagues,

Block copolymers are an essential class of polymeric materials due to their characteristic property of microphase segregation. Presently, synthesis of new block copolymers is in greater demand, given the fact that modern synthetic methods, via controlled polymerization methods, lead to materials with significant properties. Modern synthetic ways let for synthesis of block copolymers with simple or complex molecular architecture (e.g., star polymers, dendrimers). Of course, one of the major tasks that every polymer scientist has to fulfill after the synthesis of block copolymers is the verification of successful synthesis, as well as the complete reveal of the clock copolymer properties after thorough characterization, e.g., molecular, morphological characterization, or even characterization to monitor the synthesis process. Additionally in that direction, the development of new characterization methods and combination of different methods, not possible until now, positively influence the development of the block copolymer scientific field. Last, but not least, is the use of the synthesized block copolymers. There is, nowadays, a tremendous increase in applications of block copolymers, e.g., in nanotechnology, membrane science, additive industry, composites, etc.

With this in mind, I would like to invite polymer scientist from all over the world to contribute their world-class, novel, innovative and revolutionary works on any of the topics of this Special Issue of Materials, dealing with the synthesis, characterization and applications of block copolymers. Authors are welcome to submit their latest results in form of original full articles, communications or reviews.

Kind regards,

Dr. Prokopios Georgopanos
Guest Editor

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Keywords

  • block copolymers
  • star block copolymers
  • amphiphilic block copolymers
  • anionic polymerization
  • radical polymerization
  • polymerization kinetics
  • polymer characterization
  • polymer nanotechnology
  • polymer membranes
  • tailor-made polymers
  • in-situ characterization
  • polymer morphology
  • amphiphilic block copolymers
  • polymer nanostructures
  • self-assembly

Published Papers (9 papers)

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Research

Open AccessArticle
Segregation of Maghemite Nanoparticles within Symmetric Diblock Copolymer and Triblock Terpolymer Patterns under Solvent Vapor Annealing
Materials 2020, 13(6), 1286; https://doi.org/10.3390/ma13061286 - 12 Mar 2020
Abstract
Block copolymers (BCPs), through their self-assembly, provide an excellent guiding platform for precise controlled localization of maghemite nanoparticles (MNPs). Diblock copolymers (di/BCP) represent the most applied matrix to host filler components due to their morphological simplicity. A series of nanocomposites based on diblock [...] Read more.
Block copolymers (BCPs), through their self-assembly, provide an excellent guiding platform for precise controlled localization of maghemite nanoparticles (MNPs). Diblock copolymers (di/BCP) represent the most applied matrix to host filler components due to their morphological simplicity. A series of nanocomposites based on diblock copolymer or triblock terpolymer matrices and magnetic nanoparticles were prepared to study and compare the influence of an additional block into the BCP matrix. MNPs were grafted with low molecular weight polystyrene (PS) chains in order to be segregated in a specific phase of the matrix to induce selective localization. After the mixing of the BCPs with 10% w/v PS-g-MNPs, nanocomposite thin films were formed by spin coating. Solvent vapor annealing (SVA) enabled the PS-g-MNPs selective placement within the PS domains of the BCPs, as revealed by atomic force microscopy (AFM). The recorded images have proven that high amounts of functionalized MNPs can be controllably localized within the same block (PS), despite the architecture of the BCPs (AB vs. ABC). The adopted lamellar structure of the “neat” BCP thin films was maintained for MNPs loading approximately up to 10% w/v, while, for higher content, the BCP adopted lamellar morphology is partially disrupted, or even disappears for both AB and ABC architectures. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)
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Open AccessArticle
Effect of Styrene-Diene Block Copolymers and Glass Bubbles on the Post-Consumer Recycled Polypropylene Properties
Materials 2020, 13(3), 543; https://doi.org/10.3390/ma13030543 - 23 Jan 2020
Abstract
The recycled polypropylene (rPP) materials that meet technical requirements such as reducing the dimensions and improving the tensile, elongation, impact strength, thermal stability, as well as melt processing, are required for the manufacturing industry. In this paper, we studied the mechanical and thermal [...] Read more.
The recycled polypropylene (rPP) materials that meet technical requirements such as reducing the dimensions and improving the tensile, elongation, impact strength, thermal stability, as well as melt processing, are required for the manufacturing industry. In this paper, we studied the mechanical and thermal properties of post-consumer rPP by adding both synthesized thermoplastic elastomers, and glass bubbles (GB) by a melt allowing process. Styrene-butadiene (SBS) and styrene-isoprene (SIS) block-copolymers that had a styrene content of 30 wt% were synthesized by anionic sequential polymerization. The obtained post-consumer rPP composites were characterized by optical microscopy, scanning electron microscopy (SEM), mechanical analyses (tensile, density, hardness, VICAT softening temperature (VST), heat deflection temperature (HDT), dynamic mechanical analysis (DMA), IZOD strength) and thermal analyses (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)). Weight reduction and improvement of the tensile, elongation, impact strength, thermal stability, as well as melt processing of post-consumer recycled polypropylene (rPP) properties compounded with thermoplastic elastomers and glass bubbles, sustain the use of these formulations for engineering applications. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)
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Open AccessArticle
Synthesis of Poly(3-vinylpyridine)-Block-Polystyrene Diblock Copolymers via Surfactant-Free RAFT Emulsion Polymerization
Materials 2019, 12(19), 3145; https://doi.org/10.3390/ma12193145 - 26 Sep 2019
Abstract
In this work, we present a novel synthetic route to diblock copolymers based on styrene and 3-vinylpyridine monomers. Surfactant-free water-based reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of styrene in the presence of the macroRAFT agent poly(3-vinylpyridine) (P3VP) is used to synthesize diblock [...] Read more.
In this work, we present a novel synthetic route to diblock copolymers based on styrene and 3-vinylpyridine monomers. Surfactant-free water-based reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of styrene in the presence of the macroRAFT agent poly(3-vinylpyridine) (P3VP) is used to synthesize diblock copolymers with molecular weights of around 60 kDa. The proposed mechanism for the poly(3-vinylpyridine)-block-poly(styrene) (P3VP-b-PS) synthesis is the polymerization-induced self-assembly (PISA) which involves the in situ formation of well-defined micellar nanoscale objects consisting of a PS core and a stabilizing P3VP macroRAFT agent corona. The presented approach shows a well-controlled RAFT polymerization, allowing for the synthesis of diblock copolymers with high monomer conversion. The obtained diblock copolymers display microphase-separated structures according to their composition. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)
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Open AccessArticle
Adsorptive Removal of Methylene Blue from Aquatic Environments Using Thiourea-Modified Poly(Acrylonitrile-co-Acrylic Acid)
Materials 2019, 12(11), 1734; https://doi.org/10.3390/ma12111734 - 28 May 2019
Cited by 5
Abstract
The paper evaluates the adsorptive potential of thiourea-modified poly(acrylonitrile-co-acrylic acid), (TA-poly(AN-co-AA)) for the uptake of cationic methylene blue (MB) from aquatic environments via a batch system. TA-poly(AN-co-AA) polymer was synthesized through redox polymerization and modified with thiourea [...] Read more.
The paper evaluates the adsorptive potential of thiourea-modified poly(acrylonitrile-co-acrylic acid), (TA-poly(AN-co-AA)) for the uptake of cationic methylene blue (MB) from aquatic environments via a batch system. TA-poly(AN-co-AA) polymer was synthesized through redox polymerization and modified with thiourea (TA) where thioamide groups were introduced to the surface. Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), CHNS and Zetasizer were used to characterize the physico-chemical and morphological properties of prepared TA-poly(AN-co-AA). Afterwards, it was confirmed that incorporation of thioamide groups was successful. The adsorption kinetics and equilibrium adsorption data were best described, respectively, by a pseudo-second-order model and Freundlich model. Thermodynamic analysis showed the exothermic and spontaneous nature of MB uptake by TA-poly(AN-co-AA). The developed TA-poly(AN-co-AA) polymer demonstrated efficient separation of MB dye from the aqueous solution and maintained maximum adsorption capacity after five regeneration cycles. The findings of this study suggested that synthesized TA-poly(AN-co-AA) can be applied successfully to remove cationic dyes from aquatic environments. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)
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Open AccessArticle
Development and Characterization of Mechanically Durable Silicone-Polythiourethane Composites Modified with Tetrapodal Shaped ZnO Particles for the Potential Application as Fouling-Release Coating in the Marine Sector
Materials 2018, 11(12), 2413; https://doi.org/10.3390/ma11122413 - 29 Nov 2018
Cited by 3
Abstract
Ecological considerations strongly necessitate the development of environmentally friendly antifouling paints. A promising alternative to biocide containing antifouling paints are fouling-release coatings, which are non-toxic and designed to prevent permanent attachment of marine organisms to the surface, due to their low surface energy. [...] Read more.
Ecological considerations strongly necessitate the development of environmentally friendly antifouling paints. A promising alternative to biocide containing antifouling paints are fouling-release coatings, which are non-toxic and designed to prevent permanent attachment of marine organisms to the surface, due to their low surface energy. However, these coatings suffer from insufficient mechanical properties, which make them unsuitable for mechanically stressed surfaces e.g., on ship hulls. To overcome those obstacles, polydimethylsiloxane (PDMS)-polythiourethane (PTU) composites modified with tetrapodal shaped micro-nano ZnO particles (t-ZnO) were produced and characterized by evaluating the surface energy, mechanical properties, and fouling-release performance. Among all variations, PTU/1 wt.% PDMS composites with 1 wt.% t-ZnO particles possess superior properties for applications as fouling-release coatings for maritime purposes. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)
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Open AccessArticle
Amphiphilic Block Copolymer Microspheres Derived from Castor Oil, Poly(ε-carpolactone), and Poly(ethylene glycol): Preparation, Characterization and Application in Naltrexone Drug Delivery
Materials 2018, 11(10), 1996; https://doi.org/10.3390/ma11101996 - 16 Oct 2018
Cited by 4
Abstract
In the present study, the newly synthesized castor oil-derived thioether-containing ω-hydroxyacid (TEHA) block copolymers with polycaprolactone (TEHA-b-PCL), with methoxypoly(ethylene glycol) (mPEG), (TEHA-b-mPEG) and with poly(ethylene glycol) (PEG) (TEHA-b-PEG-b-TEHA), were investigated as polymeric carriers for fabrication of naltrexone (NLX)-loaded microspheres by the single emulsion [...] Read more.
In the present study, the newly synthesized castor oil-derived thioether-containing ω-hydroxyacid (TEHA) block copolymers with polycaprolactone (TEHA-b-PCL), with methoxypoly(ethylene glycol) (mPEG), (TEHA-b-mPEG) and with poly(ethylene glycol) (PEG) (TEHA-b-PEG-b-TEHA), were investigated as polymeric carriers for fabrication of naltrexone (NLX)-loaded microspheres by the single emulsion solvent evaporation technique. These microspheres are appropriate for the long-term treatment of opioid/alcohol dependence. Physical properties of the obtained microspheres were characterized in terms of size, morphology, drug loading capacity, and drug release. A scanning electron microscopy study revealed that the desired NLX-loaded uniform microspheres with a mean particle size of 5–10 µm were obtained in all cases. The maximum percentage encapsulation efficiency was found to be about 25.9% for the microspheres obtained from the TEHA-b-PEG-b-TEHA copolymer. Differential scanning calorimetry and X-ray diffractometry analysis confirmed the drug entrapment within microspheres in the amorphous state. In vitro dissolution studies revealed that all NLX-loaded formulations had a similar drug release profile: An initial burst release after 24 h, followed by a sustained and slower drug release for up to 50 days. The analysis of the release kinetic data, which were fitted into the Korsmeyer–Peppas release model, indicated that diffusion is the main release mechanism of NLX from TEHA-b-PCL and TEHA-b-mPEG microspheres, while microspheres obtained from TEHA-b-PEG-b-TEHA exhibited a drug release closer to an erosion process. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)
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Open AccessArticle
Supramolecular Networks from Block Copolymers Based on Styrene and Isoprene Using Hydrogen Bonding Motifs—Part 2: Dynamic Mechanical Analysis
Materials 2018, 11(9), 1688; https://doi.org/10.3390/ma11091688 - 12 Sep 2018
Abstract
Thermo-reversible supramolecular networks from polyisoprene-block-polystyrene-block-polyisoprene (ISI) triblock copolymers with short, functionalized polyisoprene (PI) blocks were investigated. Functional groups along the PI blocks were hydroxyl groups, ester groups with a carboxylic end-group (-O-CO-CH2-CH2-COOH), and urethane groups [...] Read more.
Thermo-reversible supramolecular networks from polyisoprene-block-polystyrene-block-polyisoprene (ISI) triblock copolymers with short, functionalized polyisoprene (PI) blocks were investigated. Functional groups along the PI blocks were hydroxyl groups, ester groups with a carboxylic end-group (-O-CO-CH2-CH2-COOH), and urethane groups with an amine end-group—synthesized from various types of diamines—(-O-CO-NH-R-NH2). Dynamic mechanical analysis (DMA) was performed at temperatures above Tg of polystyrene (PS) to investigate the influence of the different functional groups, the molecular weight, and the composition of the triblock copolymers on the materials’ properties. Furthermore, comparisons to DMA results of diblock copolymers, modified in the same way, will be presented. Arising reversible and irreversible processes observed during DMA experiments will be compared to results from temperature-dependent Fourier transform infrared (FTIR) spectroscopy. For the elaborated systems, the transition from reversible, hydrogen-bonded to permanently cross-linked networks was observed at around 150 °C. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)
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Open AccessFeature PaperArticle
Supramolecular Networks from Block Copolymers Based on Styrene and Isoprene Using Hydrogen Bonding Motifs—Part 1: Synthesis and Characterization
Materials 2018, 11(9), 1608; https://doi.org/10.3390/ma11091608 - 04 Sep 2018
Cited by 2
Abstract
The combination of controlled anionic polymerization and subsequent introduction of hydrogen bonding groups was established to form thermo-reversible, supramolecular networks. Several polyisoprene-block-polystyrene-block-polyisoprene (ISI) copolymers—with polystyrene (PS) as the main block, and consequently giving the decisive material characteristics—were synthesized. The [...] Read more.
The combination of controlled anionic polymerization and subsequent introduction of hydrogen bonding groups was established to form thermo-reversible, supramolecular networks. Several polyisoprene-block-polystyrene-block-polyisoprene (ISI) copolymers—with polystyrene (PS) as the main block, and consequently giving the decisive material characteristics—were synthesized. The novel modification approach to post-functionalize the polyisoprene (PI) end-blocks and to introduce different motifs, which are able to form self-complementary hydrogen bonds, was attained. In the first step, hydroxylation was accomplished using 9-borabicyclo[3.3.1]nonane. Starting from the hydroxylated polymer, esterification with succinic anhydride was implemented to form an ester group with carboxylic end-group (-O-CO-CH2-CH2-COOH). In a second approach, 1,1’-carbonyldiimidazole was used as coupling agent to introduce various types of diamines (diethylenetriamine, triethylentetramine, and 2,6-diaminopyridine) to prepare urethane groups with amine end-group (-O-CO-NH-R-NH2). 1H NMR spectroscopy was used to confirm the successful synthesis and to calculate the degree of functionalization Df. Differential scanning calorimetry (DSC) showed a difference of the glass transition temperature Tg between unfunctionalized and functionalized block copolymers, but no greater influence between the different types of modification, and thus, on the Tg of the PS block. In temperature dependent FTIR spectroscopy, reversible processes were observed. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)
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Open AccessFeature PaperArticle
Exploring the Self-Assembly Capabilities of ABA-Type SBS, SIS, and Their Analogous Hydrogenated Copolymers onto Different Nanostructures Using Atomic Force Microscopy
Materials 2018, 11(9), 1529; https://doi.org/10.3390/ma11091529 - 24 Aug 2018
Abstract
In this work, the self-assembled morphologies obtained for poly(styrene-b-butadiene-b-styrene) (SBS) and poly(styrene-b-isoprene-b-styrene) (SIS) ABA-type copolymers were investigated before and after hydrogenation of the polydiene block, which led to poly(styrene-b-ethylene)/poly(ethylene-b-styrene) (SEES) and poly(styrene-b-ethylene)/poly(propylene-b-styrene) (SEPS) copolymers, respectively. The evaluation of different morphologies was carried out [...] Read more.
In this work, the self-assembled morphologies obtained for poly(styrene-b-butadiene-b-styrene) (SBS) and poly(styrene-b-isoprene-b-styrene) (SIS) ABA-type copolymers were investigated before and after hydrogenation of the polydiene block, which led to poly(styrene-b-ethylene)/poly(ethylene-b-styrene) (SEES) and poly(styrene-b-ethylene)/poly(propylene-b-styrene) (SEPS) copolymers, respectively. The evaluation of different morphologies was carried out using atomic force microscopy (AFM), analyzing the effect of various parameters such as the solvent and polymer concentrations employed for film casting (toluene, cyclohexane, or tetrahydrofurane with concentrations of 1 and 3 wt%), together with that of the annealing treatment (thermal annealing at room temperature, and 60, 80, and 100 °C). The effect of these parameters in combination with the chemical nature of the polydiene block led to different morphologies with different topographic aspects affecting the roughness (Ra) of the film. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)
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