Two-dimensional (2D) materials have been demonstrated to exhibit unique properties originating from its 2D nature. In recent years, the construction of 2D materials has become a topic of great interest. This article summarizes the recent advance of 2D supramolecular organic frameworks (SOFs) which are homogeneously constructed in solution phase through self-assembly of rationally designed building blocks. These 2D SOFs are soluble and still maintain stable network structures in solutions, which exhibit uniqueness not only in structures but also in properties. In this concise review, the SOFs-related background is briefly introduced firstly, followed by outlining the research progress of soluble 2D SOFs from the perspective of monomer design, assembly, and structural characterization. The article ends with a personal outlook on the future development of this new class of supramolecular polymers.

Rare attention has been paid to the comparison between a monomer and its corresponding polymer in terms of the optoelectronic characteristics. In this article, a model H-shaped molecule and its corresponding polymer, both of which exhibited similar properties including blue emission and solution processing, were designed and synthesized. Optoelectronic properties and various kinds of stability features, including the thermostabilities, spectral stabilities and amplified spontaneous emission characteristic of the monomer and polymer were investigated. In general, the corresponding polymer PH exhibited similar optoelectronic properties but deteriorated stabilities compared with its H-shaped monomer H-1 probably owing to the similar chemical structure but the wider molecular weight distribution and metal catalyst residue. Importantly, monomer H-1 displayed a comparable ASE threshold value with its polymer PH, suggesting that H-shaped fluorene-based small molecules may be more promising optical gain media in solid state amplifers and lasers.

We present here a series of perylene diimide (PDI) based isomeric conjugated polymers for the application as efficient electron acceptors in all-polymer solar cells (all-PSCs). By copolymerizing PDI monomers with 1,4-diethynylbenzene (para-linkage) and 1,3-diethynylbenzene (meta-linkage), isomeric PDI based conjugated polymers with parallel and non-parallel PDI units inside backbones were obtained. It was found that para-linked conjugated polymer (PA) showed better solubility, stronger π-π stacking, more favorable blend morphology, and better photovoltaic performance than those of meta-linked conjugated polymers (PM) did. Device based on PTB7-Th:PA (PTB7-Th:poly{4,8-bis[5-(2-ethylhexyl)-thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)-carbonyl]thieno[3,4-b]thiophene-4,6-diyl}) showed significantly enhanced photovoltaic performance than that of PTB7-Th:MA (3.29% versus 0.92%). Moreover, the photovoltaic performance of these polymeric acceptors could be further improved via a terpolymeric strategy. By copolymerizing a small amount of meta-linkages into PA, the optimized terpolymeric acceptors enabled to enhance photovoltaic performance with improved the short-circuit current density (J_sc) and fill factor (FF), resulting in an improved power conversion efficiency (PCE) of 4.03%.

An electrochromic copolymer film of 2-(3,3-dihexyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)-7-(3,3-dihexyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-8-yl)-9H-carbazole (M1) and 4,7-bis(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (M2) was prepared via electrochemical technique. The copolymerization was performed with one to one monomer feed ratio. Electrochemical and optical properties of the resulting copolymer film (P3) and the homopolymer films of M1 and M2 (P1 and P2) were investigated by using cyclic voltammetry and UV-Vis spectrometry techniques, and the corresponding results were compared. Incorporation of M1 and M2 into copolymer matrix was clearly observed on the resulting cyclic voltammograms and UV-Vis spectra. P3 covered the visible regions coming from both P1 and P2, and exhibited a neutral state darker color than those of homopolymers. P3 film was found to have a multichromic behavior, appearing as brown in its neutral state while changing its color upon oxidation to dark-gray (at about 0.3 V), to blue (at about 0.6 V) and finally to grayish cyan (beyond 0.9 V), with a corresponding optical band gap of 1.65 eV.

The structure and kinetics of the complex formed by hyaluronic acid (HA) and poly(L-lysine) (PLL) were studied by time-resolved laser light scattering, TEM, and AFM. Because HA has a hydrophilic backbone, the complexes formed by HA and PLL are different from those formed by oppositely charged polyelectrolytes both having hydrophobic backbones. Instead of forming strong aggregates and even precipitates, the complex in the presence of excess HA is stable in the studied time period. More importantly, the complex spontaneously forms core-corona structure by the rearrangement of HA chains. The core is composed of complex rich of PLL and the corona is mainly HA. Further analysis shows that the hydrogen bond formed by HA creates a barrier hindering the further relaxation of HA chains. The automatic formation of core-corona structure by PLL/HA is helpful not only to understand the relaxation of polyelectrolyte in complex, but also to develop drug carriers with desirable properties.

A simple one-pot non-isocyanate route for synthesizing thermoplastic polyureas is presented. In situ urethanization was conducted from the ring-opening reaction of ethylene carbonate with poly(propylene glycol) bis(2-aminopropyl ether) and hexanediamine, m-xylylenediamine, or diethylene glycol bis(3-aminopropyl) ether at 100 °C for 6 h under normal pressure. Melt transurethane polycondensation was successively conducted at 170 °C under a reduced pressure of 399 Pa for different time periods. A series of non-isocyanate thermoplastic polyureas (NI-TPUreas) were prepared. The NI-TPUreas were characterized by gel permeation chromatography, FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray diffraction, atomic force microscopy, and tensile test. NI-TPUreas exhibited M_n of up to 1.67 × 10⁴ g/mol, initial decomposition temperature over 290 °C, and tensile strength of up to 32 MPa. Several crystallizable NI-TPUreas exhibited T_m exceeding 98 °C. NI-TPUreas with good thermal and mechanical properties were prepared through a green and simple one-pot non-isocyanate route.

Bilayer humidity-responsive actuators are generally composed of actuating and supporting layers of different materials with largely different wettability. Such kinds of bilayer actuators suffer from low adhesive force between the two layers during usage. This study demonstrates the preparation of humidity-responsive bilayer actuators that have the same materials in the actuating and supporting layers to avoid the adhesive issue. The bilayer actuators consist of a porous poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) layer and a nonporous PAA/PAH layer that are fabricated by exponentially layer-by-layer assembly method. At a high/low relative humidity (RH), the nonporous PAA/PAH layer can efficiently expand/shrink by absorbing/desorbing water while the volume expansion/shrinkage of the porous PAA/PAH layer in an environment with changed humidity is significantly suppressed by the micrometer-sized pores. The largely different expansion/shrinkage of the nonporous and porous PAA/PAH layers when subjected to humidity changes enables rapid and reversible rolling/unrolling motions of the bilayer actuator. The bilayer actuator shows a faster rolling speed and a larger bending curvature when subjected to a larger humidity increase.

A series of co-polyimide (PI) fibers containing phenylphosphine oxide (PPO) group were synthesized by incorporating the bis(4-aminophenoxy) phenyl phosphine oxide (DAPOPPO) monomer into the PI molecular chain followed by dry-jet wet spinning. The effects of DAPOPPO molar content on the atomic oxygen (AO) resistance of the fibers were investigated systematically. When the AO fluence increased from 0 atoms·cm⁻² to 3.2 × 10²⁰ atoms·cm⁻², the mass loss of the fibers showed the dependence on DAPOPPO molar content in co-PI fibers. The PI fiber containing 40% DAPOPPO showed lower mass loss compared to those containing 0% and 20% DAPOPPO. At higher AO fluence, the higher DAPOPPO content gave rise to dense carpet-like surface of fibers. XPS results indicated that the passivated phosphate layer was deposited on the fiber surface when exposed to AO, which effectively prevented fiber from AO erosion. With the DAPOPPO content increasing from 0% to 40%, the retentions of tensile strength and initial modulus for the fibers exhibited obvious growth from 44% to 68%, and 59% to 70%, after AO exposure with the fluence of 3.2 × 10²⁰ atoms·cm⁻². The excellent AO resistance benefits the fibers for application in low Earth orbit as flexible construction components.

Polylactide (PLA) films blended with poly(butylene adipate-co-terephthalate) (PBAT) were hot melted using a twin screw extruder with the addition of triethyl citrate (TEC) as a plasticizer and toluene diisocyanate (TDI) as a compatibilizer. The synergistic effects of the two additives on the mechanical, thermal, and morphological properties of the PLA/PBAT blend films were investigated. The influence of TEC content on the plasticized PLA films and the effect of TDI’s presence on the PLA/PBAT blend films were also studied by comparing them with neat PLA. The results showed a pronounced increase in elongation at break of the plasticized PLA films with increasing TEC levels, but a slight reduction in thermal stability. Also, the addition of TEC and TDI to the blend system not only synergistically enhanced the tensile properties and tensile-impact strength of the PLA/PBAT blends, but also affected their crystallinity and cold crystallization rate, a result of the improvement of interfacial interaction between PLA and PBAT, including the enhancement of their chain mobility. The synergy of the plasticization and compatibilization processes led to the improvement of tensile properties, tensile-impact strength, and compatibility of the blends, accelerating cold crystallization without affecting crystallization.

Phenethyl-bridged DOPO derivative (DiDOPO) was combined with graphene nanosheets (GNSs) in epoxy resin (EP) to improve its flame retardancy. The results indicated that the introduction of only 1.5 wt% DiDOPO/1.5 wt% GNS in EP increased the limited oxygen index (LOI) from 21.8% to 32.2%, hence meeting UL 94 V-0 rating. The thermogravimetric analyses revealed that char yield rose in presence of GNSs to form thermally stable carbonaceous char. The decomposition and pyrolysis products in gas phase were characterized by thermogravimetry-Fourier transform infrared spectroscopy (TG-FTIR), and the release of large amounts of phosphorus was detected in the gas phase. The evaluation of flame-retardant effect by cone calorimetry demonstrated that GNSs improved the protective-barrier effect of fire residue of EP/DiDOPO/GNS. The latter was further confirmed by digital photography and scanning electron microscopy (SEM). Also, Raman spectroscopy showed that GNSs enhanced graphitization degree of the resin during combustion. Overall, the combination of DiDOPO with GNSs provides an effective way for developing high-performance resins with improved flame retardancy.

We present here the thermodynamic investigation of in situ cascade polycondensation-coupling ring-opening polymerization (PROP) for three cyclic aromatic ester monomers, i.e., cyclic oligo(2-methyl-1,3-propylene terephthalate)s (COMPTs), cyclic oligo(neopentylene terephthalate)s (CONTs) and cyclic oligo(2-methyl-2-propyl-1,3-propylene terephthalate)s (COMPPTs). The equibrium monomer to polymer weight ratio in bulk at different polymerization temperatures for each monomer was estimated by the size exclusion chromatography (SEC), and the thermodynamic parameters were estimated by Dainton equation. Quite different from the thermodynamics of aliphatic lactones polymerization, which is an exothermic process with entropy reduction, our results showed the polymerization thermodynamics for three cyclic aromatic ester monomers was a weak exothermic process with slight entropy increment, i.e., a both enthalpy and entropy driving process. Among them, CONTs showed the largest value of enthalpy change, due to its symmetric dimethyl substitution on β-position of propandiol segments.

The nature of the crystalline phase of poly(vinylidene fluoride) (PVDF) in compatible blends with poly(ethyl methacrylate) (PEMA) was investigated by using X-ray diffraction (XRD), infrared microscopy (IR) and differential scanning calorimetry (DSC). The β phase of PVDF was observed after quenching from the melt and further annealing above the glass transition temperature over a composition range. The PVDF/PEMA blend with weight ratio of 3:2 has formed higher content of PVDF β crystals than others. By taking advantage of fast cooling rate of ultrafast differential scanning calorimeter (UFDSC), the quenching process of blends was modeled and tested simultaneously, and the melting behavior of β crystals in all blends was investigated. Three types of crystallization behavior of β phase PVDF in blends were found after quenching-annealing at different temperatures.