Mild Catalytic Degradation of Crystalline Polyethylene Units in a Solid State Assisted by Carboxylic Acid Groups.

Crystalline polyethylenes bearing carboxylic acid groups in the main chain were successfully degraded with a Ce catalyst and visible light. The reaction proceeds in a crystalline solid state without swelling in acetonitrile or water at a reaction temperature as low as 60 or 80 °C, employing dioxygen in air as the only stoichiometric reactant with nearly quantitative recovery of carbon atoms. Heterogeneous features of the reaction allowed us to reveal a dynamic morphological change of polymer crystals during the degradation.

Synthesis of Novel Polymers with Biodegradability by Main-Chain Editing of Chiral Polyketones.

Although the use of biodegradable plastics is suitable for unrecoverable, single-use plastic, their high production cost and much lower variety compared to commodity plastics limit their application. In this study, we developed a new polymer with potential biodegradability, poly(ketone/ester), synthesized from propylene and carbon monoxide. Propylene and carbon monoxide are easily available at low costs from fossil resources, and they can also be derived from biomass. Using an atom insertion reaction to the main chain of the polymer, the main-chain editing of the polymer molecule proceeded with up to 89% selectivity for atom insertion over main-chain cleavage.

Synthesis of Long-Chain Polyamides via Main-Chain Modification of Polyethyleneketones.

Long-chain polyamides (polyethyleneamides) were prepared from polyethylenes bearing in-chain carbonyl groups (polyethyleneketones) by the oxime formation and successive Beckmann rearrangement. (Diethylamino)sulfur trifluoride (DAST) was utilized as a promoter, which allowed mild conversion of the oxime group in spite of low solubility of the polymers. The polyethyleneamide exhibited different tensile property compared to a commercial HDPE.

Linking microscopic structural changes and macroscopic mechanical responses in a near-ideal bottlebrush elastomer under uniaxial deformation.

Bottlebrush (BB) elastomers, in which load-bearing network strands are densely grafted with side chains, are gaining much attention due to their unique mechanical properties. Herein, we used in situ small-angle X-ray scattering coupled with tensile tests to investigate the microscopic structural changes induced in a model BB elastomer with a controlled network structure under uniaxial deformation. The model BB elastomer was synthesized by end-linking a monodisperse star-shaped BB polymer, which ensured a controlled network structure. The BB elastomer exhibited both significant strain stiffening and backbone chain alignment under uniaxial loading, and these properties were not observed in an analogous side chain-free elastomer and gel. It was also found that the side chains in the BB elastomer did not show any sign of chain orientation even when the attached backbone chain was aligned in the stretching direction. These observations highlighted the roles of side chains: they were structurally disordered at the segment level but their steric repulsion made the backbone chain aligned and overstretched.

Quantifying the effects of cooperative hydrogen bonds between vicinal diols on polymer dynamics.

Transient cross-links such as hydrogen bonds (H-bonds) are a central concept for creating polymers with mechanical functionalities, including toughness and self-healing properties. While conventional strong H-bonding groups are based on rigid and planar molecular motifs with multidentate intermolecular interactions, we recently discovered that a structurally simple and flexible vicinal diol (VDO) could serve as a robust yet dynamic cross-link with multiple intermolecular H-bonds between hydroxy groups. In this work, we investigated the effects of cooperativity of H-bonds in VDOs on polymer dynamics. We synthesized model polybutadienes with either VDO or monool (MO) side groups by a radical-mediated thiol-ene click reaction. The oscillatory shear rheology data were analyzed by using the sticky Rouse model. The characteristic time of a single modified segment (δτ0) was significantly longer for the VDO-modified polymers than for the MO-modified polymers, even when they had the same number density of hydroxy groups. The increase in δτ0 with increasing degree of modification was much more drastic for the VDO-modified polymers than for the MO-modified polymers. Moreover, the characteristic time of an unmodified Rouse segment (τ0) was found to increase upon increasing the number of VDOs in the chain, while it was unchanged against the number of MOs. These observations highlight the cooperative effects of placing two hydroxy groups in a close vicinal arrangement. The multiplicity of H-bonds and the structural flexibility of VDOs led to efficient retardation of the chain dynamics.

A Simple and Versatile Method for the Construction of Nearly Ideal Polymer Networks.

Polymer networks usually contain numerous inhomogeneities that deteriorate their physical properties and should be eliminated to create reliable, high-performance materials. A simple method is introduced for the production of nearly ideal networks from various vinyl polymers through controlled polymerization and subsequent crosslinking. Monodisperse star polymers with bromide end groups were synthesized by atom-transfer radical polymerization and end-linked with dithiol linkers using thiol-bromide chemistry. This simple procedure formed nearly ideal polymer networks, as revealed from elasticity of the formed gel and model conjugation reactions involving linear polymers. The versatility of this method was demonstrated by preparing networks of common vinyl polymers, including polyacrylates, polymethacrylate, and polystyrene. This method can be used to prepare multiple functional nearly ideal gels and elastomers and to explore fundamental aspects of polymer networks.

Tunicate-Inspired Gallol Polymers for Underwater Adhesive: A Comparative Study of Catechol and Gallol.

Man-made glues often fail to stick in wet environments because of hydration-induced softening and dissolution. The wound healing process of a tunicate inspired the synthesis of gallol-functionalized copolymers as underwater adhesive. Copolymers bearing three types of phenolic groups, namely, phenol, catechol, and gallol, were synthesized via the methoxymethyl protection/deprotection route. Surprisingly, the newly synthesized copolymers bearing gallol groups exhibited stronger adhesive performances (typically 7× stronger in water) than the widely used catechol-functionalized copolymers under all tested conditions (in air, water, seawater, or phosphate-buffered saline solution). The higher binding strength was ascribed to the tridentate-related interfacial interaction and chemical cross-linking. Moreover, gallol-functionalized copolymers adhered to all tested surfaces including plastic, glass, metal, and biological material. In seawater, the performance of gallol-functionalized copolymer even exceeds the commercially available isocyanate-based glue. The insights from this study are expected to help in the design of biomimetic materials containing gallol groups that may be utilized as potential bioadhesives and for other applications. The results from such a kind of comparable study among phenol, catechol, and gallol suggests that tridentate structure should be better than bidentate structure for bonding to the surface.

Reversible Hydride Transfer to N,N'-Diarylimidazolinium Cations from Hydrogen Catalyzed by Transition Metal Complexes Mimicking the Reaction of [Fe]-Hydrogenase.

[Fe]-hydrogenase is a key enzyme involved in methanogenesis and facilitates reversible hydride transfer from H2 to N5,N10-methenyltetrahydromethanopterin (CH-H4MPT+). In this study, a reaction system was developed to model the enzymatic function of [Fe]-hydrogenase by using N,N'-diphenylimidazolinium cation (1+) as a structurally related alternative to CH-H4MPT+. In connection with the enzymatic mechanism via heterolytic cleavage of H2 at the single metal active site, several transition metal complex catalysts capable of such activation were utilized in the model system. Reduction of 1[BF4] to N,N'-diphenylimidazolidine (2) was achieved under 1 atm H2 at ambient temperature in the presence of an equimolar amount of NEt3 as a proton acceptor. The proposed catalytic pathways involved the generation of active hydride complexes and subsequent intermolecular hydride transfer to 1+. The reverse reaction was accomplished by treatment of 2 with HNMe2Ph+ as the proton source, where [(η5-C5Me5)Ir{(p-MeC6H4SO2)NCHPhCHPhNH}] was found to catalyze the formation of 1+ and H2 with high efficiency. These results are consistent with the fact that use of 2,6-lutidine in the forward reaction or 2,6-lutidinium in the reverse reaction resulted in incomplete conversion. By combining these reactions using the above Ir amido catalyst, the reversible hydride transfer interconverting 1+/H2 and 2/H+ was performed successfully. This system demonstrated the hydride-accepting and hydride-donating modes of biologically relevant N-heterocycles coupled with proton concentration. The influence of substituents on the forward and reverse reactivities was examined for the derivatives of 1+ and 2 bearing one para-substituted N-phenyl group.

Formation of Hierarchical Lamellae-in-Lamella Nanostructures from Polymer Blends Via Controlled Nonequilibrium Freezing.

The creation of hierarchical nanostructures in polymeric materials has been intensively studied due to the great potential to tailor their physicochemical properties. Although much success has been achieved over the past decades in block copolymers, hierarchical structure engineering in polymer blends remains a great challenge. Here, the formation of hierarchical lamellae-in-lamella nanostructures from polymer blends via controlled nonequilibrium freezing is reported. Polymer blends are first dissolved in molten hexamethylbenzene (HMB) to form a homogeneous melt. When cooled to below its melting temperature, the HMB is crystallized and depleted, and the polymers are directionally solidified. This process is rapid enough that phase separation of the polymer blends is kinetically trapped at the nanoscale level. Then, the polymer blend epitaxially crystallizes onto the HMB inside the nanophase, resulting in the hierarchical lamellae-in-lamella structure. This structure is stable under ambient conditions and tunable depending on the annealing temperature and blending ratio.

Module-Assembled Elastomer Showing Large Strain Stiffening Capability and High Stretchability.

Elastomers are indispensable materials due to their flexible, stretchable, and elastic nature. However, the polymer network structure constituting an elastomer is generally inhomogeneous, limiting the performance of the material. Here, a highly stretchable elastomer with unprecedented strain-stiffening capability is developed based on a highly homogeneous network structure enabled by a module assembly strategy. The elastomer is synthesized by efficient end-linking of a star-shaped aliphatic polyester precursor with a narrow molecular-weight distribution. The resulting product shows high strength (≈26 MPa) and remarkable stretchability (stretch ratio at break ≈1900%), as well as good fatigue resistance and notch insensitivity. Moreover, it shows extraordinary strain-stiffening capability (>2000-fold increase in the apparent stiffness) that exceeds the performance of any existing soft material. These unique properties are due to strain-induced ordering of the polymer chains in a uniformly stretched network, as revealed by in situ X-ray scattering analyses. The utility of this great strain-stiffening capability is demonstrated by realizing a simple variable stiffness actuator for soft robotics.

Effects of Alkyl Ester Chain Length on the Toughness of PolyAcrylate-Based Network Materials.

Polyacrylate-based network materials are widely used in various products owing to their facile synthesis via radical polymerization reactions. In this study, the effects of alkyl ester chains on the toughness of polyacrylate-based network materials were investigated. Polymer networks were fabricated via the radical polymerization of methyl acrylate (MA), ethyl acrylate (EA), and butyl acrylate (BA) in the presence of 1,4-butanediol diacrylate as a crosslinker. Differential scanning calorimetry and rheological measurements revealed that the toughness of MA-based networks drastically increased compared with that of EA- and BA-based networks; the fracture energy of the MA-based network was approximately 10 and 100 times greater than that of EA and BA, respectively. The high fracture energy was attributed to the glass transition temperature of the MA-based network (close to room temperature), resulting in large energy dissipation via viscosity. Our results set a new basis for expanding the applications of polyacrylate-based networks as functional materials.

A simple modification creates a great difference: new solid-base catalyst using methylated N-substituted SBA-15.

A simple modification, methylation of the nitrogen-substituted mesoporous silica SBA-15, enhances the basicity of a solid-base catalyst. The methyl group donates an electron to the nitrogen atom in the silica framework. This catalyst accelerates Knoevenagel condensation using benzaldehyde and diethyl malonate, which conventional solid-base catalysts reported to date cannot do. This report demonstrates a possible new type of base catalyst using nitrogen-substituted mesoporous silica materials.

Synthesis of a Bottlebrush Polymer Gel with a Uniform and Controlled Network Structure.

A structurally controlled polymer gel was synthesized by end-linking a monodisperse star polymer in which each arm was a bottlebrush (BB) polymer densely grafted with side chains. The combination of atom transfer radical polymerization and postpolymerization modification yielded a four-arm star-shaped BB polymer with a controlled polymerization degree of the backbone and side chains. The reactive end groups introduced at the end of each arm reacted with small bifunctional linkers in solution, leading to the formation of a BB polymer gel. The elasticity study on the BB polymer gel suggested its uniform network structure. Our method enables precise and uniform tuning of essential structural parameters across the entire BB polymer network, which will be beneficial for developing soft materials with desired mechanical responses.

Fabrication of nacre-like polymer/clay nanocomposites with water-resistant and self-adhesion properties.

HYPOTHESIS: Nacre-like polymer/clay nanocomposites are a fascinating material thanks to its superior mechanical property. However, it has been a great challenge to incorporate hydrophobic polymer components due to highly hydrophilic nature of clay, which limits further improvement of water-resistance and addition of various functionalities. To overcome this problem, we developed a method to form regular nacre-like layered structure from a hydrophobic polymer and hydrophilic clay by a combination of surface modification of clay and selective click reaction between the polymer and clay surfaces. EXPERIMENTS: Natural clay, montmorillonite, was modified with a hydrophobic surfactant bearing an ethenyl group and subsequently reacted in situ with a thiol-functionalized hydrophobic polysiloxane. The layered structure, as well as its formation process, mechanical property, physical stability in water, and self-adhesion property of the nanocomposites were investigated. FINDINGS: In situ thiol-ene click reaction between surface-modified clay and polymer led to self-alignment of clay platelets into a regular layered structure. The resultant nacre-like nanocomposites not only showed the good mechanical property but also had excellent stability in water and self-adhesion ability, both of which originated from the characteristics of the polymer used. These findings widen the possibility of functional nacre-like nanocomposites by expanding the range of applicable polymers to hydrophobic ones.

Thermoelectric Enhancement of Silicon Membranes by Ultrathin Amorphous Films.

We propose a simple, low-cost, and large-area method to increase the thermoelectric figure of merit (ZT) in silicon membranes by the deposition of an ultrathin aluminum layer. Transmission electron microscopy showed that short deposition of aluminum on a silicon substrate covers the surface with an ultrathin amorphous film, which, according to recent theoretical works, efficiently destroys phonon wave packets. As a result, we measured 30-40% lower thermal conductivity in silicon membranes covered with aluminum films while the electrical conductivity was not affected. Thus, we have achieved 40-45% higher ZT values in membranes covered with aluminum films. To demonstrate a practical application, we applied this method to enhance the performance of a silicon membrane-based thermoelectric device and measured 42% higher power generation.

Fabrication of Water-Resistant Nacre-like Polymer/Clay Nanocomposites via in Situ Polymerization.

Fabrication and characterization of water-resistant nacre-like polymer/clay nanocomposites, in which clay platelets and hydrophobic polymer chains are alternately stacked in parallel, are reported. Hydrophilic clay was converted by an ion-exchange reaction with a methacrylate monomer having a long alkyl chain and a quaternary ammonium salt group at the end. The subsequent in situ polymerization bound the neighboring clay surfaces, leading to the preferential orientation of the clay platelets owing to their high aspect ratio. The composites maintained excellent mechanical properties even after being immersed in water for more than a day. Strong shape stability was observed in water as well as in various organic solvents.

Seawater-Assisted Self-Healing of Catechol Polymers via Hydrogen Bonding and Coordination Interactions.

It is highly desirable to prevent crack formation in polymeric materials at an early stage and to extend their lifespan, particularly when repairs to these materials would be difficult for humans. Here, we designed and synthesized catechol-functionalized polymers that can self-heal in seawater through hydrogen bonding and coordination. These bioinspired acrylate polymers are originally viscous materials, but after coordination with environmentally safe, common metal cations in seawater, namely, Ca(2+) and Mg(2+), the mechanical properties of the polymers were greatly enhanced from viscous to tough, hard materials. Reduced swelling in seawater compared with deionized water owing to the higher osmotic pressure resulted in greater toughness (∼5 MPa) and self-healing efficiencies (∼80%).

Correlation between solid-state structures and enzymatic degradability of cocrystallized blends.

Solid-state structures and enzymatic degradability have been investigated for cocrystallized blends between poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [PHBV] and poly(3-hydroxybutyrate-co-3-hydroxypropionate) [PHBP]. From wide-angle X-ray diffraction patterns, small-angle X-ray scattering data, and the comparison of the enzymatic degradability of these blends, the solid-state structures of PHBV/PHBP blend samples, in which the PHBV component has higher isothermal crystal growth rate (G) value than the PHBP one, might be similar to those of the component PHBVs; while those of the PHBP/PHBV blend samples, in which PHBP component has higher G value, were similar to the component PHBPs. Normalized one-dimensional correlation functions gamma(x) of PHBV/PHBP binary blends crystallized at 90 degrees C.

Comonomer-unit compositions, physical properties and biodegradability of bacterial copolyhydroxyalkanoates.

The comonomer-unit compositions and their distribution of as-produced bacterial copolyesters, including poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxy-butyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) are described in this paper. Each copolyester sample can be comonomer-unit compositionally fractionated into several fractions, indicating that the original copolymers are mixtures of copolymers with different comonomer-unit compositions. The effects of comonomer-unit compositional distribution on thermal properties, crystallization, biodegradability and solid-state phase behavior are investigated using comonomer compositionally fractionated copolymers.

Polymers with multishape memory controlled by local glass transition temperature.

A multishape memory polymer with flexible design capabilities is fabricated by a very simple method. Local glass transition temperatures of a loosely cross-linked polymer film are changed by immersing sections of the film in a cross-linker solution with a different concentration. Each section memorizes a temporary shape, which recovers its permanent shape at a different recovery temperature depending on the local glass transition temperature. As a base polymer, we chose a network polymer prepared by a Diels-Alder reaction between poly(2,5-furandimethylene succinate) (PFS) and 1,8-bis-maleimidotriethyleneglycol (M2). Quintuple shape memory behavior was demonstrated by a PFS/M film with four sections with distinct glass transition temperatures. The number of temporary shapes was determined by the number of different M2 solutions. Furthermore, owing to the reversibility of the Diels-Alder reaction, the permanent shape was rewritable.