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Synthesis, Characterization and Applications of Block Copolymers

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

Deadline for manuscript submissions: closed (30 June 2020) | Viewed by 39547

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Dr. Prokopios Georgopanos

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Helmholtz-Zentrum Geesthacht, Zentrum für Material- und Küstenforschung GmbH, Institut für Polymerforschung, Max-Planck-Str. 1, 21502 Geesthacht, Germany
Interests: polymer membranes for gas and liquid applications; polymers and polymer membranes for hydrogen applications; mixed matrix membranes; controlled polymer synthesis; RAFT emulsion polymerization; anionic polymerization; polymer synthesis upscalling; polymerisation in continuous flow reactors; digitalization of the polymer synthesis; sustainable and more environmental friendly polymer synthesis; polymer nanotechnology; polymer morphology

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 (10 papers)

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Research

23 pages, 4013 KiB

Open AccessArticle

Synthesis, Characterization of a New Polyacrylic Acid Superabsorbent, Some Heavy Metal Ion Sorption, the Adsorption Isotherms, and Quantum Chemical Investigation

by Sevil Savaskan Yilmaz, Nuri Yildirim, Murat Misir, Yasin Misirlioglu and Emre Celik

Materials 2020, 13(19), 4390; https://doi.org/10.3390/ma13194390 - 01 Oct 2020

Cited by 13 | Viewed by 2607

Abstract

Poly(acrylic acid/Kryptofix 23-Dimethacrylate) superabsorbent polymer [P (AA/Kry23-DM) SAP] was synthesized by solution polymerization to remove Co, Ni, Cu, Cd, Mn, Zn, Pb, Cr, and Fe ions in water and improve the quality of the water. Kry23-DM cross-linker (1,4,7,13,16-Pentaoxa-10,19 diazo cyclohexene icosane di methacrylate) was synthesized using Kry23 and methacryloyl chloride. The characterization of the molecules was done by FTIR, TGA, DSC, and SEM techniques. The effects of parameters such as pH, concentration, and the metal ion interaction on the heavy metal ions uptaking of SAP was investigated. It was observed that P (AA/Kry23-DM) SAP has maximum water absorption, and the absorption increases with the pH increase. Adsorption rates and sorption capacity, desorption ratios, competitive sorption (q_cs), and distribution coefficient (log D) of P(AA/Kry23-DM) SAP were studied as a function of time and pH with the heavy metal ion concentration. Langmuir and Freundlich isotherms of the P (AA/Kry23-DM) SAP were investigated to verify the metal uptake. Molecular mechanic (MM2), Assisted Model Building with Energy Refinement (AMBER), and optimized potentials for liquid simulations (OPLS) methods. were used in quantum chemical calculations for the conformational analysis of the cross-linker and the SAP. ΔH⁰_f calculations of the cross-linker and the superabsorbent were made using Austin Model 1(AM1) method. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Applications of Block Copolymers)

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15 pages, 5148 KiB

Open AccessArticle

Segregation of Maghemite Nanoparticles within Symmetric Diblock Copolymer and Triblock Terpolymer Patterns under Solvent Vapor Annealing

by George Zapsas, Dimitrios Moschovas, Konstantinos Ntetsikas, Andreas Karydis-Messinis, Nikolaos Chalmpes, Antonios Kouloumpis, Dimitrios Gournis, Nikolaos E. Zafeiropoulos and Apostolos Avgeropoulos

Materials 2020, 13(6), 1286; https://doi.org/10.3390/ma13061286 - 12 Mar 2020

Cited by 3 | Viewed by 2344

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 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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20 pages, 4222 KiB

Open AccessArticle

Effect of Styrene-Diene Block Copolymers and Glass Bubbles on the Post-Consumer Recycled Polypropylene Properties

by Maria Râpă, Bogdan Norocel Spurcaciu, George Coman, Cristian Andi Nicolae, Raluca Augusta Gabor, Paul Niculae Ghioca, Andrei Constantin Berbecaru, Ecaterina Matei and Cristian Predescu

Materials 2020, 13(3), 543; https://doi.org/10.3390/ma13030543 - 23 Jan 2020

Cited by 9 | Viewed by 4112

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 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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14 pages, 4679 KiB

Open AccessArticle

Synthesis of Poly(3-vinylpyridine)-Block-Polystyrene Diblock Copolymers via Surfactant-Free RAFT Emulsion Polymerization

by Katharina Nieswandt, Prokopios Georgopanos, Clarissa Abetz, Volkan Filiz and Volker Abetz

Materials 2019, 12(19), 3145; https://doi.org/10.3390/ma12193145 - 26 Sep 2019

Cited by 18 | Viewed by 3939

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 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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17 pages, 3574 KiB

Open AccessArticle

Adsorptive Removal of Methylene Blue from Aquatic Environments Using Thiourea-Modified Poly(Acrylonitrile-co-Acrylic Acid)

by Abel Adekanmi Adeyi, Siti Nurul Ain Md Jamil, Luqman Chuah Abdullah, Thomas Shean Yaw Choong, Kia Li Lau and Mohammad Abdullah

Materials 2019, 12(11), 1734; https://doi.org/10.3390/ma12111734 - 28 May 2019

Cited by 48 | Viewed by 3531

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 (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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14 pages, 2947 KiB

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

by Haoyi Qiu, Iris Hölken, Anna Gapeeva, Volkan Filiz, Rainer Adelung and Martina Baum

Materials 2018, 11(12), 2413; https://doi.org/10.3390/ma11122413 - 29 Nov 2018

Cited by 30 | Viewed by 5015

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. 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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19 pages, 4632 KiB

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

by Maria Nerantzaki, Eirini Skoufa, Kyriakos-Vasileios Adam, Stavroula Nanaki, Apostolos Avgeropoulos, Margaritis Kostoglou and Dimitrios Bikiaris

Materials 2018, 11(10), 1996; https://doi.org/10.3390/ma11101996 - 16 Oct 2018

Cited by 8 | Viewed by 3819

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 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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23 pages, 4859 KiB

Open AccessArticle

Supramolecular Networks from Block Copolymers Based on Styrene and Isoprene Using Hydrogen Bonding Motifs—Part 2: Dynamic Mechanical Analysis

by Elaine Rahmstorf and Volker Abetz

Materials 2018, 11(9), 1688; https://doi.org/10.3390/ma11091688 - 12 Sep 2018

Cited by 3 | Viewed by 4456

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 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 T_g 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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22 pages, 5423 KiB

Open AccessFeature PaperArticle

Supramolecular Networks from Block Copolymers Based on Styrene and Isoprene Using Hydrogen Bonding Motifs—Part 1: Synthesis and Characterization

by Elaine Rahmstorf and Volker Abetz

Materials 2018, 11(9), 1608; https://doi.org/10.3390/ma11091608 - 04 Sep 2018

Cited by 5 | Viewed by 4962

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 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 D_f. Differential scanning calorimetry (DSC) showed a difference of the glass transition temperature T_g between unfunctionalized and functionalized block copolymers, but no greater influence between the different types of modification, and thus, on the T_g 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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21 pages, 6847 KiB

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

by Nikolaos Politakos and Galder Kortaberria

Materials 2018, 11(9), 1529; https://doi.org/10.3390/ma11091529 - 24 Aug 2018

Cited by 7 | Viewed by 3835

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 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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