ACS Macro Letters最新文献

Efficient synthesis of cyclic polymers remains a frontier challenge. We report here that macromolecular transesterification during a pseudoblock copolymerization process can be utilized for such a purpose. Organobase-catalyzed ring-opening alternating copolymerization of 3,4-dihydrocoumarin and epoxide is conducted with four-armed poly(ethylene oxide) (PEO) as a macroinitiator. Intramolecular transesterification (backbiting) occurs selectively on the newly formed polyester segments. The disconnected cyclic alternating copolymers can be easily isolated by precipitation owing to their substantial solubility difference from the PEO-containing acyclic parts. The obtained cyclic alternating copolymers exhibit low dispersity (<1.2) and a molar mass of around 3 kg mol^–1, irrespective of the monomer-to-initiator feed ratio, indicating thermodynamic control over the ring size. The macrocyclic structure is confirmed by both mass spectroscopy and microscopic visualization and then utilized to prepare cyclic-brush terpolymer by thiol–ene modification, followed by graft polymerization of propylene oxide.

Traditionally, multiple shape memory polymers (multiple-SMPs) are created by forming either immiscible blends with high phase continuity (cocontinuous or multilayer phase morphology) or miscible blends that exhibit compositional heterogeneity at the nanoscale. Here, a new strategy for the fabrication of multiple-SMPs is proposed. It consists of the possibility of homogeneous mixing of immiscible polymers in the solid state under high pressure and shear deformation conditions. The blends formed in this way exhibit homogeneity of mixing down to the nanoscale, up to 40–95 nm. The transition from immiscible to miscible blends leads to an improvement not only in shape memory but also in the mechanical performance of the blends formed. Polypropylene (PP) and polystyrene (PS) were selected as pairs of immiscible polymers. The method of solid phase mixing is high pressure torsion (HPT). It was shown that the HPT-processed 50% PP/50% PS blend is able to exhibit an excellent triple shape memory effect (shape fixation of ∼94–95%, and recovery of ∼85–95%) with widely tunable (low and high) transition temperatures.

As three-dimensional (3D) printing has emerged as a new manufacturing technology, the demand for high-performance 3D printable materials has increased to ensure broad applicability in various load-bearing structures. In particular, the thixotropic properties of materials, which allow them to flow under applied external forces but resist flowing otherwise, have been reported to enable rapid and high-resolution printing owing to their self-standing and easily processable characteristics. In this context, graphene nanosheets exhibit unique π–π stacking interactions between neighboring sheets, likely imparting self-standing capability to low-viscosity inks. Herein, we develop a thermally curable graphene-incorporated epoxy ink system that exhibits shear-thinning characteristics and upright standing capability owing to its high static yield stress (∼1,680 Pa). The reversible liquid-to-solid phase transition of the composite ink, absent in the pristine epoxy ink, is clearly identified by its viscoelastic properties and dynamic yield stress. This thixotropic composite ink enables the continuous filament printing of 10 stacked layers without the spreading of injected filaments. Significantly, the 3D-printed composite structure, post-thermal curing, exhibits robust structural integrity and is free from weld lines or voids at the stacked interfaces. Combined with the clearly elucidated processing–structure–property relationships of the ink system, our results highlight its potential for a wide spectrum of applications.

As a special kind of supramolecular compound with many favorable properties, pillar[n]arene-based supramolecular polymer networks (SPNs) show potential application in many fields. Although we have come a long way using pillar[n]arene to prepare SPNs and construct a series of smart materials, it remains a challenge to enhance the mechanical strength of pillar[n]arene-based SPNs. To address this issue, a new supramolecular regulation strategy was developed, which could precisely control the preparation of pillar[n]arene-based SPN materials with excellent mechanical properties by adjusting the polymer network structures. Specifically, we utilized the host–guest interaction between pillar[5]arene and the alkyl chain of butyl acrylate monomer to form a supramolecular polymer network and achieved the transformation of different states by regulating the cross-linking density of the polymer networks. Additionally, the polymer networks exhibited good stimuli responsiveness as well as excellent dynamic properties and reconfigurable characteristics through a temperature change and the addition of competitive hosts or guests. The research provided new possibilities for the development of polymer materials.