The formation of a poly(2,6‐carbazole) derivative during an electrochemical polymerization process is shown. Comparison of 3,5‐bis(9‐octyl‐9H‐carbazol‐2‐yl)pyridine and 3,5‐bis(9‐octyl‐9H‐carbazol‐3‐yl)pyridine by electrochemical and UV–Vis‐NIR spectroelectrochemical measurements and DFT (density functional theory) calculation prove the formation of a poly(2,6‐carbazole) derivative. Both of the compounds form stable and electroactive conjugated polymers.
A novel one‐component type II polymeric photoinitiator, poly(vinyl alcohol)–thioxanthone (PVA–TX), is synthesized by a simple acetalization process and characterized. PVA–TX enables photopolymerization of methyl methacrylate and acrylamide in both organic and aqueous media. Photopolymerization proceeds even in the absence of a co‐initiator since PVA–TX possesses both chromophoric and hydrogen donating sites in the structure.
Diarylbutadiyne derivatives are ideal monomers for providing the π‐electron‐conjugated system of polydiacetylenes (PDAs). The geometrical parameters for diacetylene topochemical polymerization are known. However, control of the molecules under these parameters is yet to be addressed. This work shows that by simply tailoring diarylbutadiyne with amide side‐chain substituents, the arrangement of the substituents and the resulting hydrogen bond framework allows formation of π‐electron‐conjugated PDA.
The sodium salt of the new bis(mesitoyl)phosphinic acid (BAPO‐OH) can be prepared in a very efficient one‐pot synthesis. It is well soluble in water and hydrolytically stable for at least several weeks. Remarkably, it acts as an initiating agent for the surfactant‐free emulsion polymerization (SFEP) of styrene to yield monodisperse, spherical nanoparticles. Time‐resolved electron paramagnetic resonance (TR‐EPR) and chemically induced electron polarisation (CIDEP) indicate preliminary mechanistic insights.
This communication reports the first example of precision polyolefin nanoalloys where an exotic immiscible polymer is nanometrically dispersed with stability in a polyolefin matrix in a highly controlled mode. Following the preparation of polypropylene/multiwalled carbon nanotubes nanocomposites (PP/MWCNTs) by in situ Ziegler‐Natta polymerization, the hydroxyl groups on the surfaces of individual MWCNTs are used to initiate ring‐opening polymerization of ε‐caprolactone, resulting in PP/poly(ε‐caprolactone) (PCL) alloy with PCL grafted on MWCNTs. Upon phase formation, the PP/MWCNTs‐g‐PCL alloys exhibit a unique PCL dispersion morphology, which is stable and solely governed by PCL molecular weight.
The chemical synthesis of a novel polyfuran, poly(2,3‐bis(hexylthio)‐[1,4]dithiino[2,3‐c]furan) ( PBDF ), substituted at the 2,3‐positions with an S‐alkylated dithiin unit, is reported. The new polymer has been characterized in terms of its electronic absorption, electrochemical, and thermal properties. Employment of the dithiin moiety provides intrinsic additional electroactivity, as well as a functional handle for substitution with alkyl groups, enhancing the processability of the polymer. The new polymer is compared with the closely related and well‐established literature compounds PEDOT and PEDTT as well‐studied, highly chalcogenated polythiophenes.
To enhance the limited degradability of poly(ethylene glycol) (PEG), a straightforward method of synthesizing poly[(ethylene glycol)‐co‐(glycolic acid)] (P(EG‐co‐GA)) via a ruthenium‐catalyzed, post‐polymerization oxyfunctionalization of various PEGs is developed. Using this method, a set of copolymers with GA compositions of up to 8 mol% are prepared with minimal reduction in molecular weight (<10%) when compared to their commercially available starting materials. The P(EG‐co‐GA) copolymers are shown to undergo hydrolysis under mild conditions.
The synthesis of tetracene‐ and pentacene‐annulated norbornadienes, formed through the Diels–Alder reaction of a dehydroacene with cyclopentadiene is reported. Ring‐opening metathesis polymerization (ROMP) leads to polymers that are investigated with respect to their physical, optical, and electronic properties by gel permeation chromatography (GPC), UV–vis spectroscopy, and cyclic voltammetry. The pentacene‐containing polymer P1 is successfully integrated into an organic field‐effect transistor (OFET); the tetracene‐containing polymer P2 is integrated into an organic light‐emitting diode (OLED).
A highly living polymer with over 100 kg mol−1 molecular weight is very difficult to achieve by controlled radical polymerization since the unavoidable side reactions of irreversible radical termination and radical chain transfer to monomer reaction become significant. It is reported that over 500 kg mol−1 polystyrene with high livingness and low dispersity could be synthesized by a facile two‐stage reversible addition–fragmentation transfer emulsion polymerization. The monomer conversion reaches 90% within 10 h. High livingness of the product is ascribed to the extremely low initiator concentration and the chain transfer constant for monomer unexpectedly much lower than the well‐accepted values in the conventional radical polymerization. The two‐stage monomer feeding policy much decreases the dispersity of the product.
Herein, the use of a 2D soft template system composed of hundred‐nanometer‐thick water/ethanol mixed layers sandwiched by lamellar bilayer membranes of a self‐assembled amphiphilic molecule to produce ultrathin polyprrole (PPy) with a uniform thickness as thin as 3.8 nm and with large dimensions (>2 μm2) is presented. The obtained PPy nanosheets exhibit regioregularity with ordered chain alignment where the polymer chains in the nanosheets produced are well aligned with a clear interchain spacing as confirmed by small‐angle X‐ray scattering measurement. The molecular‐level‐thick PPy nanosheets exhibit extremely high conductivity up to 1330 S m−1, thanks to the ordered alignment of polymer chains in the nanosheets, and a high transparency in both the visible region (transmittance >99%) and near‐infrared region (transmittance >93%).
The synthesis of an ambipolar π‐conjugated copolymer consisting of alternating diketopyrrolopyrrole and tetrafluorobenzene via direct arylation polymerization (DAP) is reported. Two different combinations of monomers are investigated under various catalytic conditions for DAP. The target polymer obtained under an optimized catalytic condition shows minimal structural defects, a number‐average molecular weight of 33.2 kDa, and balanced electron and hole mobility of 1 × 10−2 cm2 V−1 S−1 in the organic field‐effect transistors fabricated and tested under ambient conditions.
Cross‐linked azobenzene liquid‐crystalline polymer films with a poly(oxyethylene) backbone are synthesized by photoinitiated cationic copolymerization. Azobenzene moieties in the film surface toward the light source are simultaneously photoaligned during photopolymerization with unpolarized 436 nm light and thus form a splayed alignment in the whole film. The prepared films show reversible photoinduced bending behavior with opposite bending directions when different surfaces of one film face to ultraviolet light irradiation.
Ethylene–propylene–methyl methacrylate (MMA) and ethylene–hexene–MMA A‐B‐C block copolymers with high molecular weight (>100 000) are synthesized using fluorenylamide‐ligated titanium complex activated by modified methylaluminoxane and 2,6‐di‐tert‐butyl‐4‐methylphenol for the first time. After diblock copolymerization of olefin is conducted completely, MMA is added and activated by aluminum Lewis acid to promote anionic polymerization. The length of polyolefin and poly (methyl methacrylate) (PMMA) is controllable precisely by the change of the additive amount of olefin and polymerization time, respectively. A soft amorphous polypropylene or polyhexene segment is located between two hard segments of semicrystalline polyethylene and glassy PMMA blocks.
A facile method for the aqueous synthesis of monodisperse and micronmeter‐sized colloids with highly carboxylated surfaces is presented. The method is applied to three different monomers, styrene, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate, and illustrate tuning of the size and monodispersity in the reactions. High surface density of carboxylic acids of up to 10 COOH nm−2 from potentiometric titrations, is achieved through copolymerization with itaconic acid. The versatility of this system is highlighted by creating highly fluorescent and monodisperse particles that can be index matched in aqueous solution and through surface modification via the carboxylic acid groups using standard amidation chemistry.
To overcome drug delivery issues associated with its short half‐life in vivo, p‐coumaric acid (pCA), a naturally occurring bioactive, has been chemically incorporated into a poly(anhydride‐ester) backbone through solution polymerization. Nuclear magnetic resonance and Fourier transform infrared spectroscopies indicated that pCA was successfully incorporated without noticeable alterations in structural integrity. The polymer's weight‐average molecular weight and thermal properties were determined, exhibiting a molecular weight of over 26 000 Da and a glass transition temperature of 57 °C. In addition, in vitro hydrolytic release studies demonstrated pCA release over 30 d with maintained antioxidant activity, demonstrating the polymer's potential as a controlled release system.
A chemically cross‐linked but remarkably (re)processable shape‐memory polymer (SMP) is designed by cross‐linking poly(ε‐caprolactone) (PCL) stars via the efficient triazolinedione click chemistry, based on the very fast and reversible Alder–ene reaction of 1,2,4‐triazoline‐3,5‐dione (TAD) with indole compounds. Typically, a six‐arm star‐shaped PCL functionalized by indole moieties at the chain ends is melt‐blended with a bisfunctional TAD, directly resulting in a cross‐linked PCL‐based SMP without the need of post‐curing treatment. As demonstrated by the stress relaxation measurement, the labile character of the TAD–indole adducts under stress allows for the solid‐state plasticity reprocessing of the permanent shape at will by compression molding of the raw cross‐linked material, while keeping excellent shape‐memory properties.
The different mechanisms contributing to adhesion between two polymer surfaces are summarized and described in individual examples, which represent either seminal works in the field of adhesion science or novel approaches to achieve polymer–polymer adhesion. A further objective of this article is the development of new methodologies to achieve strong adhesion between low surface energy polymers.
Hierarchical self‐assembly of transient composite hydrogels is demonstrated through a two‐step, orthogonal strategy using nanoparticle tectons interconnected through metal–ligand coordination complexes. The resulting materials are highly tunable with moduli and viscosities spanning many orders of magnitude, and show promising self‐healing properties, while maintaining complete optical transparency.
In this communication, a mild, efficient, and generalized polycondensation route is developed for poly(disulfide)s from commercially available monomers 2,2′‐dithiodipyridine and 1,6‐hexanedithiol. Using the stoichiometric imbalance between the two monomers, it is possible to produce telechelic poly(disulfide)s of predictable molecular weight with reactive pyridyl disulfide groups at both the terminals of the chain. The two terminal pyridyl disulfide groups can be quantitatively replaced by a functional thiol using selective thiol‐disulfide exchange and thus produces functional telechelic poly(disulfide)s, which can be used as a macroinitiator to initiate ring‐opening polymerization of a cyclic lactide monomer generating an ABA‐type triblock copolymer with degradable B block.
A new method for fabricating hydrogels with intricate control over hierarchical 3D porosity using microfiber porogens is presented. Melt electrospinning writing of poly(ε‐caprolactone) is used to create the sacrificial template leading to hierarchical structuring consisting of pores inside the denser poly(2‐oxazoline) hydrogel mesh. This versatile approach provides new opportunities to create well‐defined multilevel control over interconnected pores with diameters in the lower micrometer range inside hydrogels with potential applications as cell scaffolds with tunable diffusion and transport of, e.g., nutrients, growth factors or therapeutics.
