The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazene bases. In addition, the commercially relevant double-metal cyanide (DMC) catalyst systems are discussed. Besides the synthetic progress, new types of multifunctional linear PEG (mf-PEG) and PPO structures accessible by copolymerization of EO or PO with functional epoxide comonomers are presented as well as complex branched, hyperbranched, and dendrimer like polyethers. Amphiphilic block copolymers based on PEO and PPO (Poloxamers and Pluronics) and advances in the area of PEGylation as the most important bioconjugation strategy are also summarized. With the ever growing toolbox for epoxide polymerization, a "polyether universe" may be envisaged that in its structural diversity parallels the immense variety of structural options available for polymers based on vinyl monomers with a purely carbon-based backbone.

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Poly(ethylene glycol) (PEG) is a widely used biocompatible polymer. We describe a novel epoxide monomer with methyl-thioether moiety, 2-(methylthio)ethyl glycidyl ether (MTEGE), which enables the synthesis of well-defined thioether-functional poly(ethylene glycol). Random and block mPEG-b-PMTEGE copolymers (Mw/Mn = 1.05-1.17) were obtained via anionic ring opening polymerization (AROP) with molecular weights ranging from 5 600 to 12 000 g·mol(-1). The statistical copolymerization of MTEGE with ethylene oxide results in a random microstructure (rEO = 0.92 ± 0.02 and rMTEG E = 1.06 ± 0.02), which was confirmed by in situ (1)H NMR kinetic studies. The random copolymers are thermoresponsive in aqueous solution, with a wide range of tunable transition temperatures of 88 to 28 °C. In contrast, mPEG-b-PMTEGE block copolymers formed well-defined micelles (Rh ≈ 9-15 nm) in water, studied by detailed light scattering (DLS and SLS). Intriguingly, the thioether moieties of MTEGE can be selectively oxidized into sulfoxide units, leading to full disassembly of the micelles, as confirmed by detection of pure unimers (DLS and SLS). Oxidation-responsive release of encapsulated Nile Red demonstrates the potential of these micelles as redox-responsive nanocarriers. MTT assays showed only minor effects of the thioethers and their oxidized derivatives on the cellular metabolism of WEHI-164 and HEK-293T cell lines (1-1000 μg·mL(-1)). Further, sulfonium PEG polyelectrolytes can be obtained via alkylation or alkoxylation of MTEGE, providing access to a large variety of functional groups at the charged sulfur atom.

Polyamic acid (PAA) salts are amenable to photocuring additive manufacturing processes of all-aromatic polyimides. Due to an all-aromatic structure, these high-performance polymers are exceptionally chemically and thermally stable but are not conventionally processable in their imidized form. The facile addition of 2-(dimethylamino)ethyl methacrylate (DMAEMA) to commercially available poly(4,4′-oxydiphenylene pyromellitamic acid) (PMDA-ODA PAA) afforded ultraviolet curable PAA salt solutions. These readily prepared solutions do not require multistep synthesis, exhibited fast gel times (<5 s), and rendered high G′ gel-state moduli. Vat photopolymerization 3D printing afforded self-supporting organogels. Subsequent thermal treatment rendered the cross-linked PAA precursor to all-aromatic PMDA-ODA polyimide. This fast and facile strategy makes PMDA-ODA polyimides accessible in three dimensions and offers impact on aerospace or automotive technologies.

Amine-functional poly(ethylene glycol) (PEG) copolymers have been prepared that exhibit thermo- and pH- responsive behavior in aqueous solution. Three novel tertiary di(n-alkyl)glycidylamine monomers have been introduced for anionic ring-opening copolymerization (AROcP) with ethylene oxide (EO): N,N-di(n-butyl)glycidylamine (DButGA), N,N-di(n-hexyl)glycidylamine (DHexGA), and N,N-di(n-octyl)glycidylamine (DOctGA). Via controlled AROcP we synthesized well-defined (M w/M n = 1.05–1.14), water-soluble block- and gradient-type PEG copolymers, containing up to 25 mol % of the respective dialkylglycidylamine comonomer. Molecular weights ranged from 4900 to 12 000 g mol–1. Detailed in-situ 1H NMR kinetics and 13C triad analyses elucidate the microstructures of the copolymers and the relative reactivity of the novel comonomers. Notably, the n-alkyl chain length had no significant influence on the relative reactivity of the glycidylamine comonomers. Calculated reactivity ratios ranged from r EO = 1.84, r DButGA = 0.49 to r EO = 1.78, r DOctGA = 0.42, manifesting the formation of gradient copolymers. Thermo- and pH-responsive properties of these copolymers are precisely tunable by the comonomer ratio, and cloud points in aqueous solution can be adjusted between 21 and 93 °C. Electron paramagnetic resonance (EPR) spectroscopic studies with TEMPO as a spin probe were conducted to elucidate host–guest interactions of the copolymers. Unexpectedly, the n-alkyl chain length of the different glycidylamine comonomers only influences the inverse phase transition of the gradient copolymers, but not of the block copolymers on the nanoscale. Self-assembly of the block- and gradient-type copolymers in aqueous alkaline solution by both static and dynamic light scattering has also been investigated after confirming the existence of pure unimers in methanol.

All-aromatic polyimides have degradation temperatures above 500 °C, excellent mechanical strength, and chemical resistance, and are thus ideal polymers for high-temperature applications. However, their all-aromatic structure impedes additive manufacturing (AM) because of the lack of melt processability and insolubility in organic solvents. Recently, our group demonstrated the design of UV-curable polyamic acids (PAA), the precursor of polyimides, to enable their processing using vat photopolymerization AM. This work leverages our previous synthetic strategy and combines it with the high solution viscosity of nonisolated PAA to yield suitable UV-curable inks for UV-assisted direct ink write (UV-DIW). UV-DIW enabled the design of complex three-dimensional structures comprising of thin features, such as truss structures. Dynamic mechanical analysis of printed and imidized specimens confirmed the thermomechanical properties typical of all-aromatic polyimides, showing a storage modulus above 1 GPa up to 400 °C. Processing polyimide precursors via DIW presents opportunity for multimaterial printing of multifunctional components, such as three-dimensional integrated electronics.

Both homo-and copolymerization of the hitherto nonpolymerizable epoxide monomer epicyanohydrin (EPICH) with ethylene oxide (EO) have been studied, employing the monomer activation technique. Tetraoctylammonium bromide or tetrabutylammonium iodide was used as initiator combined with i-Bu 3 Al to activate the EPICH monomer. The EPICH content was varied from 4 to 16 mol %, yielding well-defined PEG-co-PEPICH copolymers with molecular weights M n (SEC) ranging from 3700 to 8800 g mol −1 . The nitrile groups of the resulting polyethers were further reduced or hydrolyzed to introduce amino, amide, or carboxyl groups at the polyether backbone, circumventing protecting group chemistry. Successful transformation of the functional groups was proven by SEC measurements, 1 H NMR, 13 C NMR, and FT-IR spectroscopy. These carboxyl-functional PEG copolymers are anionic polyelectrolytes consisting only of purely aliphatic polyether structures with carboxyl groups. The hydrolyzed PEPICH homopolymers represent the first polyether-based analogues of poly(acrylamide) and poly(acrylic acid). In pronounced contrast to poly(acrylic acid), carboxylfunctional PEPICH shows excellent aqueous solubility even at low pH.

Detailed understanding of the monomer distribution in copolymers is essential to tailor their properties. For the first time, we have been able to utilize in situ 1H NMR spectroscopy to monitor the monomer-activated anionic ring opening copolymerization (AROP) of ethylene oxide (EO) with a glycidyl ether comonomer, namely, ethoxy ethyl glycidyl ether (EEGE). We determine reactivity ratios and draw a direct comparison to conventional oxyanionic ROP. Surprisingly, the respective monomer reactivities differ strongly between the different types of AROP. Under conventional oxyanionic conditions similar monomer reactivities of EO and EEGE are observed, leading to random structures (r EO = 1.05 ± 0.02, r EEGE = 0.94 ± 0.02). Addition of a cation complexing agent (18-crown-6) showed no influence on the relative reactivity of EO and EEGE (r EO = r EEGE = 1.00 ± 0.02). In striking contrast, monomer-activated AROP produces very different monomer reactivities, affording strongly tapered copolymer structures (r EO = 8.00 ± 0.16, r EEGE = 0.125 ± 0.003). These results highlight the importance of understanding reactivity ratios of comonomer pairs under certain polymerization conditions, at the same time demonstrating the ability to generate both random and strongly tapered P­(EO-co-EEGE) polyethers by simple one-pot statistical anionic copolymerization. These observations may be generally valid for the copolymerization of EO and glycidyl ethers.