Effect of the Substituent Position on the Anionic Copolymerization of Styrene Derivatives: Experimental Results and Density Functional Theory Calculations

In a combined synthetic, kinetic and theoretical study, the living anionic copolymerization of styrene and its ring-methylated derivatives ortho-, meta-, and para-methylstyrene (MS) was examined by real-time 1H NMR spectroscopy in the nonpolar solvents toluene-d8 and cyclohexane-d12 as well as by density functional theory calculations. Based on the NMR kinetics data, reactivity ratios for each comonomer pair were determined by the Kelen–Tudős method and numerical integration of the copolymerization equation (Contour software). The reaction pathway was modeled and followed by density functional theory (DFT) calculations to validate and predict the experimentally derived reactivity ratios. Un…

Catechol Acetonide Glycidyl Ether (CAGE): A Functional Epoxide Monomer for Linear and Hyperbranched Multi-Catechol Functional Polyether Architectures

A protected catechol-containing epoxide monomer, catechol acetonide glycidyl ether (CAGE), is introduced. CAGE is conveniently obtained in three steps and enables the incorporation of surface-active catechol moieties into a broad variety of hydrophilic and biocompatible polyether architectures by copolymerization. Via acidic cleavage of the acetal protecting groups, the polymer-attached catechol functionalities are liberated and available for surface attachment or metal complexation. CAGE has been copolymerized with ethylene oxide and glycidol to obtain both linear poly(ethylene glycol) and hyperbranched polyglycerol copolymers, respectively, with multiple surface-adhesive catechol moieties…

Copolymerization of Isoprene with p-Alkylstyrene Monomers: Disparate Reactivity Ratios and the Shape of the Gradient

The statistical copolymerization of isoprene with p-ethyl- (p-ES), p-isopropyl- (p-iPS), and p-tert-butylstyrene (p-tBS) initiated by sec-butyllithium in cyclohexane was investigated with respect to kinetics, reactivity ratios, and formation of tapered block copolymers with pronounced monomer gradient. An efficient synthetic route to the monomers was developed on a multigram scale, relying on the precipitation of the side-product triphenylphosphine oxide at low temperature. The copolymerization kinetics and resulting molecular weight distributions were analyzed. The dispersity, Đ, of the copolymers depends on the p-alkyl substituent, the the degree of polymerization Pn and the comonomer mol…

Tapered copolymers of styrene and 4‐vinylbenzocyclobutene via carbanionic polymerization for crosslinkable polymer films

Tetrahydrofuran: More than a “Randomizer” in the Living Anionic Copolymerization of Styrene and Isoprene: Kinetics, Microstructures, Morphologies, and Mechanical Properties

The statistical anionic copolymerization of isoprene (I) and styrene (S) is commonly used to synthesize tapered block copolymers, enabling control of the phase behavior by adjusting the order–disor...

Multifunctional Fe(III)-Binding Polyethers from Hydroxamic Acid-Based Epoxide Monomers.

Multiple hydroxamic acids are introduced at poly(ethylene glycol) (PEG) via copolymerization of ethylene oxide with a novel epoxide monomer containing a 1,4,2-dioxazole-protected hydroxamic acid (HAAGE). AB- and ABA-type di- and triblock copolymers as well as statistical copolymers of HAAGE and ethylene oxide are prepared in a molecular weight range between 2600 and 12 000 g mol-1 with low dispersities (Ð < 1.2). Cleavage of the acetal protecting group after the polymerization is achieved by mild acidic treatment, releasing multiple free hydroxamic acids tethered to the polyether backbone. The chelation properties of different polymer architectures (statistical versus diblock and ABA triblo…

Celebrating 100 years of “polymer science”: Hermann Staudinger's 1920 manifesto

The first translation into English of Hermann Staudinger's seminal 1920 paper ‘On polymerisation’, to mark its 100 year anniversary.

Hydroxamic Acid: An Underrated Moiety? Marrying Bioinorganic Chemistry and Polymer Science

Even 150 years after their discovery, hydroxamic acids are mainly known as the starting material for the Lossen rearrangement in textbooks. However, hydroxamic acids feature a plethora of existing and potential applications ranging from medical purposes to materials science, based on their excellent complexation properties. This underrated functional moiety can undergo a broad variety of organic transformations and possesses unique coordination properties for a large variety of metal ions, for example, Fe(III), Zn(II), Mn(II), and Cr(III). This renders it ideal for biomedical applications in the field of metal-associated diseases or the inhibition of metalloenzymes, as well as for the separ…

Local and Subchain Relaxation of Polyisoprene in Multiblock Copolymers with a Tapered Interface

We report on the local and (sub-) chain dynamics in a new class of tapered multiblock copolymers synthesized by the repeated statistical living anionic copolymerization of a mixture of isoprene and...

Tunable dynamic hydrophobic attachment of guest molecules in amphiphilic core–shell polymers

In this study, synthesis and dynamic properties of amphiphilic core–shell polymers are reported as monitored through their interaction with small amphiphilic molecules. Brush-like structures are formed with a hydrophobic core surrounded by a hydrophilic shell utilizing controlled radical addition–fragmentation chain transfer (RAFT) polymerization of macromonomers consisting of linear polyglycerol chains attached to alkylene methacrylate. Continuous wave electron paramagnetic resonance (CW EPR) spectroscopy is employed to study how the amphiphilic, paramagnetic spin probe 16-DSA (16-doxyl stearic acid) interacts with polymers of different alkylene chain lengths in their hydrophobic cores and…

Kinetics of Anionic Living Copolymerization of Isoprene and Styrene Using in Situ NIR Spectroscopy: Temperature Effects on Monomer Sequence and Morphology

The living anionic copolymerization of isoprene (I) and styrene (S) can afford a variety of different polymer microstructures that strongly depend on experimental parameters such as solvent, counte...

Two-photon absorption dye based on 2,5-bis(phenylacrylonitrile)thiophene with aggregration enhanced fluorescence

This paper reports the synthesis and characterization of a 2,5-bis(phenylacrylonitrile) thiophene based two-photon dye, designed to show enhancement in fluorescence quantum yield in nanoaggregated form. Strong solvatochromism has been observed and explained by the favoritism of locally excited (LE) or internal charge transfer (ICT) state depending on the solvent polarity. Aqueous dispersions of nanoparticles have been prepared and investigated regarding their optical properties which were correlated to the LE and ICT state and the molecular structure of the aggregates. (C) 2016 Optical Society of America

One-Step Block Copolymer Synthesis versus Sequential Monomer Addition: A Fundamental Study Reveals That One Methyl Group Makes a Difference

Block copolymers of polyisoprene and polystyrene are key materials for polymer nanostructures as well as for several commercially established thermoplastic elastomers. In a combined experimental and kinetic Monte Carlo simulation study, the direct (i.e., statistical) living anionic copolymerization of a mixture of isoprene (I) and 4-methylstyrene (4MS) in nonpolar media was investigated on a fundamental level. In situ 1H NMR spectroscopy enabled to directly monitor gradient formation during the copolymerization and to determine the nature of the gradient. In addition, a precise comparison with the established copolymerization of isoprene and styrene (I/S) was possible. Statistical copolymer…

A general concept for the introduction of hydroxamic acids into polymers.

Polyethers (PEG) with hydroxamic acid groups enable chelation of a variety of metal ions, coating of metal oxide surfaces and stabilization of nanoparticles. In contrast to catechol, hydroxamic acids are oxidation stable and biocompatible.

Polymerization of long chain alkyl glycidyl ethers: a platform for micellar gels with tailor-made melting points

Controlled polymerization of long-chain alkyl glycidyl ethers (AlkGE) under anionic ring opening polymerization conditions is enabled by the addition of a crown ether (18-crown-6, K+). Homopolymers with molecular weights in the range of 4000 to 9000 g mol−1 and side chain melting temperatures of 14 °C (C12-AlkGE) and 43 °C (C16-AlkGE), respectively were synthesized. Furthermore, a series of amphiphilic ABA polyether triblock copolymers with polyethylene glycol (PEG) as the hydrophilic central block (Mn = 6k, 10k, and 20k g mol−1) with total molecular weights in the range of 7000 to 28 000 g mol−1 and narrow dispersity (1.12 to 1.34) were prepared. Separate melting endotherms of the triblock…

Multi-olefin containing polyethers and triazolinediones: a powerful alliance

Multi-functional polyethers with ene or diene moieties were prepared via the polymerisation of tailored functional glycidyl ether monomers to create a platform for click chemistry with triazolinediones (TADs). Specifically, two novel monomers (i) 2,4-hexadien-1-yl glycidyl ether (HDEGE) and (ii) citronellyl glycidyl ether (CitroGE), designed to undergo a Diels–Alder or Alder–Ene reaction with TADs, respectively, were synthesized and subsequently transformed into a variety of tailored polyethers, either via the monomer activated method or anionic ring opening polymerisation. Multi-functional copolymers of HDEGE with ethylene oxide, propylene oxide and ethoxy ethyl glycidyl ether as well as A…

Isoprene/Styrene Tapered Multiblock Copolymers with up to Ten Blocks: Synthesis, Phase Behavior, Order, and Mechanical Properties

The living anionic copolymerization of isoprene and styrene in cyclohexane affords tapered block copolymers due to the highly disparate reactivity ratios of rI = 12.8 and rS = 0.051. Repeated addit...