Non-Equilibrium Blockcopolymer Self-Assembly

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (30 September 2015) | Viewed by 58702

Special Issue Editor

Laboratory for Organic and Macromolecular Chemistry, Institut für Organische Chemie und Makromolekulare Chemie, Friedrich-Schiller-Universität, Jena IOMC Humboldtstr. 10, D-07743 Jena, Germany
Interests: polymer synthesis; block copolymers; self-assembly; interpolyelectrolyte complexation; stimuli-responsive materials; membranes
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Special Issue Information

Dear Colleagues,

The last decades have witnessed great and (sometimes) unpredicted progress in the generation of sophisticated nanostructures from block copolymers in different microenvironments such as the solution state, in thin-films, or as bulk materials. Besides the wide variety of available building blocks, one intriguing feature of block copolymer self-assembly is that one single material can adopt different morphologies, depending on the surrounding conditions. Subtle changes in the environment, suitable additives, crystallization occurring, confinement, or simply changes in the solvent sequence or the temperature (pathway) during self-assembly can lead to the formation of kinetically trapped nanostructures. In some cases, this even enables the hierarchical organization of well-defined soft matter building blocks over several length scales.

In that respect, this issue is intended to highlight recent advances concerning all aspects of non-equilibrium block copolymer self-assembly as well as possible applications in diverse fields like, e.g., materials science, biotechnology, or supramolecular chemistry.

Prof. Dr. Felix H. Schacher
Guest Editor

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Published Papers (6 papers)

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Research

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549 KiB  
Article
Fabrication of CO2 Facilitated Transport Channels in Block Copolymer through Supramolecular Assembly
by Yao Wang, Ying Shang, Xianwu Li, Tong Tian, Longcheng Gao and Lei Jiang
Polymers 2014, 6(5), 1403-1413; https://0-doi-org.brum.beds.ac.uk/10.3390/polym6051403 - 14 May 2014
Cited by 18 | Viewed by 8801
Abstract
In this paper, the molecule 12-amidine dodecanoic acid (M) with ending groups of carboxyl and amidine groups respectively was designed and synthesized as CO2-responsive guest molecules. The block copolymer polystyrene-b-polyethylene oxide (PS-b-PEO) was chosen as the host [...] Read more.
In this paper, the molecule 12-amidine dodecanoic acid (M) with ending groups of carboxyl and amidine groups respectively was designed and synthesized as CO2-responsive guest molecules. The block copolymer polystyrene-b-polyethylene oxide (PS-b-PEO) was chosen as the host polymer to fabricate a composite membrane through H-bonding assembly with guest molecule M. We attempted to tune the phase separation structure of the annealed film by varying the amount of M added, and investigated the nanostructures via transmission electron microscope (TEM), fourier transform infrared (FT-IR) etc. As a result, a reverse worm-like morphology in TEM image of bright PS phase in dark PEO/M matrix was observed for PS-b-PEO/M1 membrane in which the molar ratio of EO unit to M was 1:1. The following gas permeation measurement indicated that the gas flux of the annealed membranes dramatically increased due to the forming of ordered phase separation structure. As we expected, the obtained composite membrane PS-b-PEO/M1 with EO:M mole ratio of 1:1 presented an evident selectivity for moist CO2 permeance, which is identical with our initial proposal that the guest molecule M in the membranes will play the key role for CO2 facilitated transportation since the amidine groups of M could react reversibly with CO2 molecules in membranes. This work provides a supramolecular approach to fabricating CO2 facilitated transport membranes. Full article
(This article belongs to the Special Issue Non-Equilibrium Blockcopolymer Self-Assembly)
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5676 KiB  
Article
Morphologies and Thermal Variability of Patterned Polymer Films with Poly(styrene-co-maleic anhydride)
by Pieter Samyn and Gustaaf Schoukens
Polymers 2014, 6(3), 820-845; https://0-doi-org.brum.beds.ac.uk/10.3390/polym6030820 - 14 Mar 2014
Cited by 7 | Viewed by 8606
Abstract
Patterned films of poly(styrene-co-maleic anhydride) copolymers were deposited by dip-coating from acetone solutions. A qualitative study of the film morphologies shows the formation of polymer spheres with smaller diameters at higher amounts of maleic anhydride (MA), and long-fibrous features at higher [...] Read more.
Patterned films of poly(styrene-co-maleic anhydride) copolymers were deposited by dip-coating from acetone solutions. A qualitative study of the film morphologies shows the formation of polymer spheres with smaller diameters at higher amounts of maleic anhydride (MA), and long-fibrous features at higher molecular weights. Upon heating, the films progressively re-assemble with short- and long-fibrous structures as a function of heating time and temperature. In parallel, the film morphologies are quantified by image processing and filtering techniques. The differential scanning calorimetry confirms the higher glass transition temperatures with increasing amount of MA. The analysis with Raman spectroscopy shows interactions between the molecules in solution and effects of ring-opening (hydrolysis) and ring-closure (formation of MA) during drying of the films. The water contact angles on the patterned films are within the hydrophilic range. They mainly correlate with the amount of MA moieties calculated from spectroscopy, while the roughness parameters have a minor effect. The variations in film patterns illustrate the self-assemble ability of the copolymers and confirm a heterogeneous molecular structure, as previously assumed. Full article
(This article belongs to the Special Issue Non-Equilibrium Blockcopolymer Self-Assembly)
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2122 KiB  
Article
Synthesis and Solution Properties of Double Hydrophilic Poly(ethylene oxide)-block-poly(2-ethyl-2-oxazoline) (PEO-b-PEtOx) Star Block Copolymers
by Tobias Rudolph, Sarah Crotty, Moritz Von der Lühe, David Pretzel, Ulrich S. Schubert and Felix H. Schacher
Polymers 2013, 5(3), 1081-1101; https://0-doi-org.brum.beds.ac.uk/10.3390/polym5031081 - 02 Sep 2013
Cited by 24 | Viewed by 9183
Abstract
We demonstrate the synthesis of star-shaped poly(ethylene oxide)-block-poly(2-ethyl-2-oxazoline) [PEOm-b-PEtOxn]x block copolymers with eight arms using two different approaches, either the “arm-first” or the “core-first” strategy. Different lengths of the outer PEtOx blocks ranging from [...] Read more.
We demonstrate the synthesis of star-shaped poly(ethylene oxide)-block-poly(2-ethyl-2-oxazoline) [PEOm-b-PEtOxn]x block copolymers with eight arms using two different approaches, either the “arm-first” or the “core-first” strategy. Different lengths of the outer PEtOx blocks ranging from 16 to 75 repeating units were used, and the obtained materials [PEO28-b-PEtOxx]8 were characterized via size exclusion chromatography (SEC), nuclear magnetic resonance spectroscopy (NMR), and Fourier-transform infrared spectroscopy (FT-IR) measurements. First investigations regarding the solution behavior in water as a non-selective solvent revealed significant differences. Whereas materials synthesized via the “core-first” method seemed to be well soluble (unimers), aggregation occurred in the case of materials synthesized by the “arm-first” method using copper-catalyzed azide-alkyne click chemistry. Full article
(This article belongs to the Special Issue Non-Equilibrium Blockcopolymer Self-Assembly)
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3237 KiB  
Article
Supramolecular Assemblies from Poly(styrene)-block-poly(4-vinylpyridine) Diblock Copolymers Mixed with 6-Hydroxy-2-naphthoic Acid
by Bhavesh Bharatiya, Jean-Marc Schumers, Elio Poggi and Jean-François Gohy
Polymers 2013, 5(2), 679-695; https://0-doi-org.brum.beds.ac.uk/10.3390/polym5020679 - 05 Jun 2013
Cited by 17 | Viewed by 9358
Abstract
Supramolecular assemblies involving interaction of a small organic molecule, 2-hydroxy-6-Naphthoic acid (HNA), with poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymers are utilized to obtain micellar structures in solution, nanostructured thin films on flat substrates and, finally, nanoporous thin films. The formation of [...] Read more.
Supramolecular assemblies involving interaction of a small organic molecule, 2-hydroxy-6-Naphthoic acid (HNA), with poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymers are utilized to obtain micellar structures in solution, nanostructured thin films on flat substrates and, finally, nanoporous thin films. The formation of hydrogen bonds between HNA and the poly(4-vinylpyridine) (P4VP) blocks is confirmed by spectroscopic measurements. The accordingly P4VP/HNA hydrogen-bonded complexes are poorly soluble in 1,4-dioxane, resulting in the formation of micellar structures with a P4VP/HNA core and a polystyrene (PS) corona. Those micelles have been spin-coated onto silicon wafers, resulting in nanostructured thin films consisting of P4VP/HNA dot-like features embedded in a PS matrix. The morphology of those films has been tuned by solvent annealing. Selective dissolution of HNA by methanol results in the formation of a nanoporous thin film. The P4VP/HNA nanodomains have been also cross-linked by borax, and the thin films have been further dissolved in a good solvent for PS, leading to micelles with a structure reminiscent of the thin films. Full article
(This article belongs to the Special Issue Non-Equilibrium Blockcopolymer Self-Assembly)
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Review

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8423 KiB  
Review
Crystallization Behaviors and Structure Transitions of Biocompatible and Biodegradable Diblock Copolymers
by Feifei Xue and Shichun Jiang
Polymers 2014, 6(8), 2116-2145; https://0-doi-org.brum.beds.ac.uk/10.3390/polym6082116 - 04 Aug 2014
Cited by 8 | Viewed by 7471
Abstract
Biocompatible and biodegradable block copolymers (BBCPs) containing crystalline blocks become increasingly important in polymer science, and have great potential applications in polymer materials. Crystallization in polymers is accompanied by the adoption of an extended conformation, or often by chain folding. It is important [...] Read more.
Biocompatible and biodegradable block copolymers (BBCPs) containing crystalline blocks become increasingly important in polymer science, and have great potential applications in polymer materials. Crystallization in polymers is accompanied by the adoption of an extended conformation, or often by chain folding. It is important to distinguish between crystallization in homopolymers and in block copolymers. In homopolymers, chain folding leads to metastable structures introduced by the crystallization kinetics. In contrast, equilibrium chain folding in diblocks can be achieved as the equilibrium number of the folds is controlled by the size of the second block. The structures of BBCPs, which are determined by the competition between crystallization, microphase separation, kinetics and processing, have a tremendous influence on the final properties and applications. In this review, we present the recent advances on crystalline–crystalline diblock copolymer in our group. Full article
(This article belongs to the Special Issue Non-Equilibrium Blockcopolymer Self-Assembly)
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751 KiB  
Review
Precise Synthesis of Block Polymers Composed of Three or More Blocks by Specially Designed Linking Methodologies in Conjunction with Living Anionic Polymerization System
by Yuri Matsuo, Ryuji Konno, Takashi Ishizone, Raita Goseki and Akira Hirao
Polymers 2013, 5(3), 1012-1040; https://0-doi-org.brum.beds.ac.uk/10.3390/polym5031012 - 17 Jul 2013
Cited by 48 | Viewed by 14456
Abstract
This article reviews the successful development of two specially designed linking methodologies in conjunction with a living anionic polymerization system for the synthesis of novel multiblock polymers, composed of three or more blocks, difficult to be synthesized by sequential polymerization. The first methodology [...] Read more.
This article reviews the successful development of two specially designed linking methodologies in conjunction with a living anionic polymerization system for the synthesis of novel multiblock polymers, composed of three or more blocks, difficult to be synthesized by sequential polymerization. The first methodology with the use of a new heterofunctional linking agent, 2-(4-chloromethylphenyl)ethyldimethylchlorosilane (1), was developed for the synthesis of multiblock polymers containing poly(dimethylsiloxane) (PDMS) blocks. This methodology is based on the selective reaction of the chain-end silanolate anion of living PDMS, with the silyl chloride function of 1, and subsequent linking reaction of the resulting ω-chain-end-benzyl chloride-functionalized polymer with either a living anionic polymer or living anionic block copolymer. With this methodology, various multiblock polymers containing PDMS blocks, up to the pentablock quintopolymer, were successfully synthesized. The second methodology using an α-phenylacrylate (PA) reaction site was developed for the synthesis of multiblock polymers composed of all-vinyl polymer blocks. In this methodology, an α-chain-end-PA-functionalized polymer or block copolymer, via the living anionic polymerization, was first prepared and, then, reacted with appropriate living anionic polymer or block copolymer to link the two polymer chains. As a result, ACB (BCA), BAC (CAB), (AB)n, (AC)n, ABA, ACA, BCB, and ABCA multiblock polymers, where A, B, and C were polystyrene, poly(2-vinylpyridine), and poly(methyl methacrylate) segments, could be successfully synthesized. The synthesis of triblock copolymers, BAB, CAC, and CBC, having molecular asymmetry in both side blocks, was also achieved. Furthermore, the use of living anionic polymers, derived from many other monomers, categorized as either of styrene, 2-vinylpyridine, or methyl methacrylate in monomer reactivity, in the linking methodology enabled the number of synthetically possible block polymers to be greatly increased. Once again, all of the block polymers synthesized by these methodologies are new and cannot be synthesized at all by sequential polymerization. They were well-defined in block architecture and precisely controlled in block segment. Full article
(This article belongs to the Special Issue Non-Equilibrium Blockcopolymer Self-Assembly)
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