One Decade of Microwave‐Assisted Polymerizations: Quo vadis?

The application of microwave irradiation in polymer syntheses and modifications is of continuously growing interest and has received significant international interest since the beginning of the millennium. Preceded by a review that was published 6 years ago, the present paper summarizes the most recent trends in this research area. Radical as well as step‐growth and ring‐opening polymerizations will be addressed; furthermore, the evolution from microwave‐assisted polymerizations to microwave‐assisted material fabrication will be described on the examples of polymeranalogous reactions, polymer/metal composites and bio‐based materials.

     

Fabrication of Au/Titania Composite Nanodot Arrays from Au‐Loaded Block Copolymer Micellar Films

Summary: A simple route to an ordered array of metal/semiconductor oxide composite nanodots is presented. Micellar monolayer films of polystyrene‐block‐poly(2‐vinyl pyridine) (PS‐b‐P2VP) loaded with HAuCl₄ in the P2VP nanodomains are used as templates. TiO₂ is generated selectively within the polar P2VP domains of PS‐b‐P2VP/HAuCl₄ films by chemical vapor deposition of TiCl₄. Subsequent removal of the organic matrix by oxygen plasma or UV light leads to an array of Au/TiO₂ composite nanoparticles on the substrate surface.

Schematic illustration of the process to fabricate an array of Au/titania composite nanodots.     

Au/CdS Hybrid Nanoparticles in Block Copolymer Micellar Shells

A polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) micellar structure with a P2VP core containing 5 nm CdS nanoparticles (NPs) and a PS shell formed in toluene that is a good solvent for PS block undergoes the core‐shell inversion by excess addition of methanol that is a good solvent for P2VP block. It leads to the formation of micellar shell‐embedded CdS NPs in the methanol major phase. The spontaneous crystalline growth of Au NPs on the CdS surfaces positioned at micellar shells without a further reduction process is newly demonstrated. The nanostructure of Au/CdS/PS‐b‐P2VP hybrid NPs is confirmed by transmission electron microscopy, energy‐dispersive X‐ray, and UV‐Vis absorption.

     

Linear Azo Polymer Containing Conjugated 5,5′‐Azodisalicylic Acid Segments in the Main Chain: Synthesis,Characterization, and Degradation

Summary: Copolymers of poly(ethylene oxide) (PEO) and 5,5′‐azodisalicylic acid (Olsalazine, OLZ) were synthesized and evaluated by hydrolysis and in‐vitro biodegradation with azoreductase. It was found that changing the molecular weight of the PEO blocks affected the loading ratio of OLZ, and resulted in significant differences in the hydration and degradability of the copolymers. These novel azo‐containing copolymers can be used in colon‐specific drug delivery.

Release of 5‐ASA from OLZ and PEO‐OLZ copolymers incubated with rat cecum content in the presence of benzyl viologen and α‐D ‐glucose.     

Transparent and Conductive Polyethylene Oxide Film by the Introduction of Individualized Single‐Walled Carbon Nanotubes

It is demonstrated that an optically transparent and electrically conductive polyethylene oxide (PEO) film is fabricated by the introduction of individualized single‐walled carbon nanotubes (SWNTs). The incorporated SWNTs in the PEO film sustain their intrinsic electronic and optical properties and, in addition, the intrinsic properties of the polymer matrix are retained. The individualized SWNTs with smaller diameter provide high transmittance as well as good electrical conductivity in PEO films.

     

A High‐Content Diarylethene Photochromic Polymer for an Efficient Fluorescence Modulation

Summary: A highly fluorescent photochromic polymer, poly‐BTFO4, was prepared. The fluorescence quantum yield of the poly‐BTFO4 was six times higher than that of BTFO4. Fatigue resistance of the polymer at its photostationary state was significantly enhanced compared with that of BTFO4. Importantly, the poly‐BTFO4 film also showed an efficient photochromism as well as strong fluorescence similar to the results in solution, which allow photoinduced fluorescence switching applicable to optical switches.

Improvement of fluorescence quantum yield and fatigue resistance.     

Highly Asymmetric Phase Diagram of a Poly(1,2‐octylene oxide)–Poly(ethylene oxide) Diblock Copolymer System Comprising a Brush‐Like Poly(1,2‐octylene oxide) Block

The phase diagram of a series of poly(1,2‐octylene oxide)–poly(ethylene oxide) (POO–PEO) diblock copolymers is determined by small‐angle X‐ray scattering. The Flory–Huggins interaction parameter was measured by small‐angle neutron scattering. The phase diagram is highly asymmetric due to large conformational asymmetry that results from the hexyl side chains in the POO block. Non‐lamellar phases (hexagonal and gyroid) are observed near f_PEO = 0.5, and the lamellar phase is observed for f_PEO ≥ 0.5.

     

Light‐Responsive Block Copolymers

Stimuli‐responsive polymers are the subject of intense research because they are able to show responses to various environmental changes. Among those stimuli, light has attracted much attention since it can be localized in time and space and it can also be triggered from outside of the system. In this paper, we review light‐responsive block copolymers (LRBCs) that combine characteristic features of block copolymers, e.g., self‐assembly behavior, and light‐responsive systems. The different photo‐responsive moieties that have been incorporated so far in block copolymers as well as the proposed applications are discussed.

     

A Novel Route for Fabricating Metal‐Polymer Composite Nanoparticles with Phase‐Separated Structures

Au nanoparticles (NPs) and polymer composite particles with phase‐separation structures were prepared based on phase separation structures. Au NPs were successfully synthesized in amphiphilic block‐copolymer micelles, and then composite particles were formed by a simple solvent evaporation process from Au NPs and polymer solution. The phase separated structures (Janus and Core‐shell) were controlled by changing the combination of polymers having differing hydrophobicity.

     

Submicron Polymer Gratings: Optical Diffraction and Spontaneous Brillouin Scattering

Summary: Brillouin light scattering (BLS) from submicron‐size patterned polyurethane (PU) films was found to display rich spectral features. Their identification allows the determination of the mechanical properties of the PU and the characterization of the periodicity and the coherence of the structure. A temperature‐dependent study demonstrates that BLS is a sensitive tool to monitor changes of the mechanical properties and/or of the morphology.

(a) Scheme of the sample structure and the scattering geometry, (b) SEM top view of the PU features.     

A Superhydrophobic Surface Fabricated by an Electrostatic Process

We describe the fabrication of a biomimically designed superhydrophobic poly(ε‐caprolactone) surface, which was obtained using a modified electrostatic process. The fabricated surface exhibits a micron‐sized pyramid structure consisting of accumulated droplets and nanofibres. By using this simple one‐step process, we can achieve a superhydrophobic surface having both a high water contact angle and low threshold sliding angle, similar to that of the superhydrophobic plant leaf.

     

Emulsion‐Induced Ordered Microporous Films Based on Micelles of Amphiphilic Poly(ethylene oxide)‐block‐Poly(methyl methacrylate) Diblock Copolymers

Well‐defined PEO‐b‐PMMA was prepared, initiated by macroinitiator PEO‐Br, by means of ATRP, where esterification of the terminal hydroxyl group of PEO with 2‐bromoisobutyryl bromide yielded a macroinitiator PEO‐Br. Highly ordered microporous films (hexagonal pattern) were constructed by emulsion micelles of such amphiphilic diblock copolymer formed from a solution with CHCl₃/H₂O/THF = 100:5:10 (v/v). We also constructed the microporous films using diblock copolymer by the current water‐assisted method.

     

Synthesis of a Novel ABC Triblock Copolymer with a Rigid‐Rod Block via Atom Transfer Radical Polymerization

Summary: A novel ABC triblock copolymer with a rigid‐rod block was synthesized by atom transfer radical polymerization (ATRP). First, a poly(ethylene oxide) (PEO)‐Br macroinitiator was synthesized by esterification of PEO with 2‐bromoisobutyryl bromide, which was subsequently used in the preparation of a poly(ethylene oxide)‐block‐poly(methyl methacrylate) (PEO‐b‐PMMA) diblock copolymer by ATRP. A poly(ethylene oxide)‐block‐poly(methyl methacrylate)‐block‐poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene} (PEO‐b‐PMMA‐b‐PMPCS) triblock copolymer was then synthesized by ATRP using PEO‐b‐PMMA as a macroinitiator.

ABC triblock copolymer with a rigid‐rod block.     

High Rate Silicification of Peptide‐Polymer Assemblies Toward Composite Nanotapes

Well‐defined silica composite nanofibers are generated in a silicification process of self‐assembled poly(ethylene oxide)‐peptide nanotapes. Inspired by biological silica morphogenesis processes the nanotapes exhibit strong binding capabilities for silicic acid. Thus, pre‐hydrolyzed tetramethoxysilane could be used as silica precursor. Very low concentrations (270 µM) and short contact times (10 s) are sufficient to form effectively integrated nano‐composite tapes.

     

Combining Steric and Electrostatic Stabilization Using Hydrophilic MacroRAFT Agents in an Ab Initio Emulsion Polymerization of Styrene

Hydrophilic (co)polymers carrying a thiocarbonyl thio end group such as poly(dimethylaminoethyl methacrylate), poly(ethylene oxide), and poly(ethylene oxide)‐block‐poly(dimethylaminoethyl methacrylate) have been evaluated as precursors of stabilizers in batch ab initio emulsion polymerization of styrene under acidic conditions to form electrosterically stabilized polystyrene latex particles. As a mixture of P(DMAEMA/H⁺Cl⁻)‐RAFT and PEO‐RAFT failed to give satisfactory results, PEO‐RAFT was used as a control agent for the RAFT polymerization of DMAEMA, and the resulting block copolymer was successfully used in ab initio styrene emulsion polymerization.

     

Functionalization of Crosslinked Vesicles by Co‐Self‐Assembly of a Gelable Diblock Copolymer and Mercaptosilane

Herein, a convenient and general method to simultaneously fix and functionalize polymeric vesicles with sulphydryl groups by the co‐self‐assembly of poly(ethylene oxide)‐block‐poly[3‐(triethoxysilyl)propyl methacrylate] (PEO‐b‐PTESPMA) and 3‐mercaptopropyltrialkoxysilane in an aqueous solution is reported. The presence of sulphydryl groups across the vesicle membrane has been confirmed by using an energy‐filtered technique during TEM analysis and by capturing Au nanoparticles.

     

Nanofibers by Green Electrospinning of Aqueous Suspensions of Biodegradable Block Copolyesters for Applications in Medicine,Pharmacy and Agriculture

Poly(hexamethylene adipate)‐PEO block copolymers (PHA‐b‐PEO) with different PEO contents were synthesized and processed to aqueous suspensions with high solid contents by a solvent displacement method followed by dialysis. The best suspension displayed a solid content of 16 wt.‐% and an average particle size of 108 nm. This suspension was mixed with a small amount of high molecular weight PEO and Brij78 and electrospun into corresponding nanofibers. After extraction with water, nanofibers of PHA‐b‐PEO were obtained. Electrospinning of aqueous suspensions of biodegradable polyesters alleviates concerns regarding safety, toxicology and environmental problems, which are associated with spinning of such polyesters from harmful organic solvents and thereby offers novel perspectives for applications in medicine, pharmacy and agriculture. Electrospinning of polymers from aqueous suspensions avoiding harmful organic solvents is suggested to be “green electrospinning”.

     

Synthesis,Characterization and Self‐Assembly of Novel Amphiphilic Block Copolymers with a Polyhedral Oligomeric Silsesquioxanes Moiety Attached at the Junction of the Two Blocks

A novel well‐defined amphiphilic block copolymer, with the polyhedral oligomeric silsesquioxane (POSS) moiety at the junction of the two blocks of polystyrene and poly(ethylene oxide) (PEO), was designed and synthesized. First, a macroinitiator containing a POSS moiety and a PEO chain was prepared and then atom transfer radical polymerization of styrene was carried out in the presence of the macroinitiator in bulk. The polymerization results show that the process bears the characteristics of controlled/living free radical polymerizations. The structure and molecular weight of the polymers were characterized by GPC, ¹H NMR, and FT‐IR spectroscopy. The self‐assembly behaviors of the polymers was investigated by TEM and SEM. It was observed that the polymers can self‐assemble into vesicles in aqueous solution.

     

Controlling Fusion and Aggregation in Polymersome Dispersions

The effects of addition of poly(ethylene oxide) (PEO) to poly(ethylene oxide)₁₆‐block‐poly(butylene oxide)₂₂ (EB1) polymersome dispersions has been studied. Aggregation and membrane fusion between polymersomes were observed with great control of the outcome by varying PEO molecular weight. Small‐scale fusion of 2 to 3 polymersomes was seen with low‐molecular‐weight PEO, whilst large‐scale aggregation occurred above a critical PEO molecular weight of 4 000 Da. The resulting highly porous EB1‐PEO aggregate shows great promise for applications in cell entrapment for transport and delivery, and as a three‐dimensional scaffold for use in tissue engineering.