Brush‐First ROMP of poly(ethylene oxide) macromonomers of varied length: impact of polymer architecture on thermal behavior and Li+ conductivity

The properties of polymeric materials are dictated not only by their composition but also by their molecular architecture. Here, by employing brush‐first ring‐opening metathesis polymerization (ROMP), norbornene‐terminated poly(ethylene oxide) (PEO) macromonomers ( MM‐n , linear architecture), bottlebrush polymers ( Brush‐n , comb architecture), and brush‐arm star polymers ( BASP‐n , star architecture), where n indicates the average degree of polymerization (DP) of PEO, are synthesized. The impact of architecture on the thermal properties and Li⁺ conductivities for this series of PEO architectures is investigated. Notably, in polymers bearing PEO with the highest degree of polymerization, irrespective of differences in architecture and molecular weight (~100‐fold differences), electrolytes with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as an Li⁺ source exhibit normalized ionic conductivities (σ_n) within only 4.9 times difference (σ_n = 29.8 × 10^?5 S cm^?1 for MM‐45 and σ_n = 6.07 × 10^?5 S cm^?1 for BASP‐45 ) at a concentration of Li⁺ r = [Li⁺]/[EO] = 1/12 at 50 °C. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 448–455     

Generalizing Rosenbluth's Algorithm to Include Along‐the‐Chain Intramolecular Energies

We incorporate the Boltzmann factors for inter‐monomer bending energy into the monomer growth direction choice in Rosenbluth's algorithm to model chains of arbitrary nearest‐neighbor rigidity. This allows for the consideration of compact (bent state lower in energy), free (straight and bent state equal in energy), or extended chains (bent state higher). We validate against, and compare to, various other results, showing very good agreement with known results for short chains and demonstrate the ability to model chains up to 500 segments long, far beyond the length at which the normal Rosenbluth method becomes unstable for reasonable nonzero bending energies. This approach is easily generalizable both to other energies determinable during chain growth, for example, polymers composed of more than one type of monomer with differing monomer interaction energies, as well as to other chain production algorithms. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1684–1691     

From Glucose to Polymers: A Continuous Chemoenzymatic Process

Efforts to synthesize degradable polymers from renewable resources are deterred by technical and economic challenges; especially, the conversion of natural building blocks into polymerizable monomers is inefficient, requiring multistep synthesis and chromatographic purification. Herein we report a chemoenzymatic process to address these challenges. An enzymatic reaction system was designed that allows for regioselective functional group transformation, efficiently converting glucose into a polymerizable monomer in quantitative yield, thus removing the need for chromatographic purification. With this key success, we further designed a continuous, three-step process, which enabled the synthesis of a sugar polymer, sugar poly(orthoester), directly from glucose in high yield (73 % from glucose). This work may provide a proof-of-concept in developing technically and economically viable approaches to address the many issues associated with current petroleum-based polymers.     

Crystallization-Driven Asymmetric Helical Assembly of Conjugated Block Copolymers and the Aggregation Induced White-light Emission and Circularly Polarized Luminescence

Controlling the self-assembly morphology of π-conjugated block copolymer is of great interesting. Herein, amphiphilic poly(3-hexylthiophene)-block-poly(phenyl isocyanide)s (P3HT-b-PPI) copolymers composed of π-conjugated P3HT and optically active helical PPI segments were readily prepared. Taking advantage of the crystallizable nature of P3HT and the chirality of the helical PPI segment, crystallization-driven asymmetric self-assembly (CDASA) of the block copolymers lead to the formation of single-handed helical nanofibers with controlled length, narrow dispersity, and well-defined helicity. During the self-assembly process, the chirality of helical PPI was transferred to the supramolecular assemblies, giving the helical assemblies large optical activity. The single-handed helical assemblies of the block copolymers exhibited interesting white-light emission and circularly polarized luminescence (CPL). The handedness and dissymmetric factor of the induced CPL can be finely tuned through the variation on the helicity and length of the helical nanofibers.     

A Robust Mixed-Lanthanide PolyMOF Membrane for Ratiometric Temperature Sensing

Temperature sensors play a significant role in biology, chemistry, and engineering, especially those that can work accurately in a noninvasive manner. We adopted a photoinduced post-synthetic copolymerization strategy to realize a membranous ratiometric luminescent thermometer based on the emissions of two lanthanide ions. This novel mixed-lanthanide polyMOF membrane exhibits not only the integrity and temperature sensing behaviour of the Ln-MOF powder but also excellent mechanical properties, such as flexibility, elasticity, and processability. Moreover, the polyMOF membrane shows remarkable stability under harsh conditions, including high humidity, strong acid and alkali (pH 0–14), which allowed the mapping of temperature distributions in extreme circumstances. This work highlights a simple strategy for polyMOF membrane formation and pushes forward the further practical application of Ln-MOF-based luminescent thermometers in various fields and conditions.     

Numerical Simulation of the Distribution Function and Free Energy of a Single Wormlike Polymer Confined between Hard Walls

We focus on the distribution and free energy of a wormlike polymer confined between two parallel hard walls.The variation in the distribution and free energy of the wormlike chain as the spacing between the walls decreases(or as the total contour length of the wormlike chain increases or as the persistence length of the chain increases)is simulated.The main reason for these changes is a degradation of the long wormlike chain into a Gaussian long chain under weak confinement.     

Optical diffusers based on uniform nano-sized polymer balls/nematic liquid crystals composite films

ABSTRACT

Optical diffusers are promising diffusing materials in the optical devices such as monitors, projectors, fibre optics, light-emitting diode (LED) systems and liquid crystal displays (LCDs). We report optical diffusers comprising uniformly distributed nano-sized polymer balls/nematic liquid crystals (LCs) by ultraviolet (UV) click reaction of ene monomer and thiol monomer. By optimising the mass ratio 1:1 of ene and thiol, of which the average diameter of the corresponding nano-sized polymer balls is about 900 nm, relatively high optical transmission and haze with 88.99% and 94.49% are yielded, respectively. Furthermore, by controlling the curing time, the average diameter of nano-sized polymer balls can be reduced to 810 nm, and the developed film exhibits high transmission (98.49%) without sacrificing the high haze (91.77%). This paper demonstrates that UV click reaction is an economical approach to fabricate optical diffusers in a controllable manner.     

Synthesis and characterization of novel ferrocenyl glycidyl ether polymer,ferrocenyl poly (epichlorohydrin) and ferrocenyl poly (glycidyl azide)

Poly (ferrocenyl glycidyl ether) was synthesized by polymerization of 2-[(4-ferrocenylbutoxy)methyl]oxirane (FcEpo) using toluene solution of methylaluminoxane as the catalyst. Copolymerization of 2-[(4-ferrocenylbutoxy)methyl]oxirane with epichlorohydrin was used for the synthesis of another ferrocenyl based poly (epichlorohydrin). Ferrocenyl based poly (glycidyl azide), GAP, was synthesized by treatment of sodium azide with this copolymer in DMF as solvent at room temperature. The synthesized ferrocenyl based polymers were characterized by FT-IR, ¹HNMR, UV–Vis, TGA, DSC and GPC analysis. The UV–Vis spectra of synthesized polymers show the absorption band of ferrocene moiety at about 450 nm. The TGA and DSC analysis show that poly (ferrocenyl glycidyl ether) has good thermal stability. The TGA analysis shows that the copolymerization of 2-[(4-ferrocenylbutoxy)methyl]oxirane with epichlorohydrin improved the thermal stability of the copolymer. The GPC analysis of poly (ferrocenyl glycidyl ether), ferrocenyl based poly (epichlorohydrin) and Ferrocenyl based poly (glycidyl azide) show the PDI between 1.14–1.17. The electrochemical behavior of synthesized polymers was investigated by cyclic voltammetry (CV) measurements. The CV curves of synthesized polymers show good electrochemical performance and there is one redox system with the single-electron reversible reaction that associated with ferrocene moiety in polymers structure. The anodic and cathodic peak currents increased with scan rate confirmed redox reactions in the system are kinetically fast diffusion-controlled reactions.     

Ultrasound-assisted nanoscaled supramolecular coordination polymer as an efficient recyclable catalyst for photocatalytic degradation of dye pollutants

An ultrasound-assisted nanoscaled supramolecular coordination polymer (nanosized 1′ ) has been synthesized using a self-assembly reaction of K₃[Cu (CN)₄] and hexamethylenetetramine in the presence of Me₃SnCl under ambient conditions. Nanosized 1′ was examined using elemental analysis, Fourier transform–infrared, transmission electron microscopy, scanning electron microscopy and X-ray powder diffractions. It was structurally compared with the single crystal supramolecular coordination polymer ^∞₃[Cu₆(CN)₇(C₆H₁₂N₄)₂(OH₃)]; SCP 1. The photocatalytic activities of nanosized 1′ and SCP 1 toward different hazardous organic dyes were determined under ambient, UV-light irradiation and ultrasonic conditions. SCP 1 and nanosized 1′ as heterogeneous nanoparticles catalysts exhibited high catalytic activity for degradation of Congo Red, Methyl Violet 2B and Methylene Blue dyes. The effects of operational parameters on catalytic degradation process, identification of the degradation products and recycling of the catalyst were also investigated. SCP 1 and nanosized 1′ are recyclable heterogeneous catalysts and can be reused with efficient activities. The mechanism of degradation using different scavenger techniques iss proposed and discussed. The catalytic oxidation process is mainly caused by ^•OH radicals.     

Pd nanoparticles supported on amphiphilic porous organic polymer as an efficient catalyst for aqueous hydrodechlorination and Suzuki-Miyaura coupling reactions

Developing efficient and recyclable heterogeneous catalysts for organic reactions in water is important for the sustainable development of chemical industry. In this work, Pd nanoparticles supported on DABCO-functionalized porous organic polymer was successfully prepared through an easy copolymerization and successive immobilization method. Characterization results indicated that the prepared catalyst featured big surface area, hierarchical porous structure, and excellent surface amphiphilicity. We demonstrated the use of this amphiphilic catalyst in two case reactions, i.e. the aqueous hydrodechlorination and Suzuki-Miyaura coupling reactions. Under mild reaction conditions, the catalyst showed high catalytic activities for the two reactions. In addition, the catalyst could be easily recovered and reused for several times. Also, no obvious Pd leaching and aggregation of Pd nanoparticles occurred up during the consecutive reactions.