Chinese Journal of Polymer Science最新文献

Recent experimental observations of knotting in DNA and proteins have stimulated the simulation studies of polymer knots. Simulation studies usually identify knots in polymer conformations through the calculation of the Alexander polynomial. However, the Alexander polynomial cannot directly discriminate knot chirality, while knot chirality plays important roles in many physical, chemical, and biological properties. In this work, we discover a new relationship for knot chirality and accordingly, develop a new algorithm to extend the applicability of the Alexander polynomial to the identification of knot chirality. Our algorithm adds an extra step in the ordinary calculation of the Alexander polynomial. This extra step only slightly increases the computational cost. The correctness of our algorithm has been proved mathematically by us. The implication of this algorithm in physical research has been demonstrated by our studies of the tube model for polymer knots. Without this algorithm, we would be unable to obtain the tubes for polymer knots.

Polyimide (PI) is widely used in high-frequency communication technology due to its exceptional comprehensive properties. However, traditional PI has a relatively elevated dielectric constant and dielectric loss. Herein, the different cross-linked structures were introduced in PI matrix and conducted a detailed discussion on the influence of cross-linking agent content and cross-linking structure type on the overall performance of PI films. In comparison to the dielectric constant of 2.9 of neat PI, PI with an interchain cross-linking structure containing 2 wt% 1,3,5-tris(4-aminophenyl)benzene (TAPB) (interchain-PI-2) exhibited the reduced dielectric constant of 2.55 at 1 MHz. The PI films with intrachain cross-linking structure containing 2 wt% TAPB (intrachain-PI-2) exhibited the lowest dielectric constant of 2.35 and the minimum dielectric loss of 0.0075 at 1 MHz. It was due to the more entanglement junctions of intrachain-PI resulting in decreased carrier transport. The thermal expansion coefficients of both interchain-PI and intrachain-PI films were effectively reduced. Moreover, in contrast to interchain-PI films, the intrachain-PI films maintained colorlessness and transparency as the cross-linking agent content increased. This work compared the effects of two different cross-linked structures on the performance of PI films and provided a feasible way to obtain low-k PI films with excellent comprehensive performance for 5G applications.

Metal-backboned polymers with anisotropy microstructures are promising for conductive, optoelectronic, and magnetic functional materials. However, the structure-property relationships governing the interplay between the chemical structure and electromagnetic property of the metal-backboned polymer have been rarely investigated. Here we report a carbon/nickel hybrid from metal-backboned polymer to serve as electromagnetic wave-absorbing materials, which exhibit high microwave absorption capacity and tunable absorption band. The presence of nickel backbones promote the generation of heterogeneous interfaces with carbon during calcination, thereby enhancing the wave-absorbing capacity of the carbon/nickel hybrid. The C/Ni hybrids show a minimal reflection loss of −49.1 dB at 13.04 GHz, and its frequency of the absorption band can be adjusted by controlling the thickness of the absorption layer.

Electrospun nanofibrous separators, despite lacking superior mechanical strength, have gained widespread attention with high porosity and facile processing. Herein, utilizing the fact that thermal imidization temperature of poly(amic acid) (PAA) into polyimide (PI) coincides with the pre-oxidation temperature of polyacrylonitrile (PAN) into carbon fiber, we proposed a new cross-electrospinning strategy to obtain a composite nanofibrous separator (PI/oPAN) randomly interwoven by PI and pre-oxidized PAN (oPAN) nanofibers, via synchronously electrospinning the PAA and PAN onto the same collector and then heat-treating for 2 h at 300 °C. The resultant PI/oPAN separator was able to preserve high porosity (71.7%), electrolyte wettability and thermal stability of PI nanofibrous membrane, and surprisingly exhibited high mechanical strength, being 3 times of PI, which mainly because of the numerous adhesion points generated by the melting of PAN in the pre-oxidation process. Meanwhile, the polar groups of oPAN and 3D fibrous network enhanced the PI/oPAN separator’s ionic conductivity and Li⁺ transference number, rendering the corresponding cell with more stable cycling performance than cells assembled with pure PI, PAN or commercial PP separator. Therefore, this work might provide a new avenue for the ongoing design and further development of LIB separators capable of high safety and high performance.

Hydrogen bonds (H-bonds) are the most essential non-covalent interactions in nature, playing a crucial role in stabilizing the secondary structures of proteins. Taking inspiration from nature, researchers have developed several multiple H-bonds crosslinked supramolecular polymer materials through the incorporation of H-bond side-chain units into the polymer chains. N-acryloyl glycinamide (NAGA) is a monomer with dual amides in the side group, which facilitates the formation of multiple dense intermolecular H-bonds within poly(N-acryloyl glycinamide) (PNAGA), thereby exhibiting diverse properties dependent on concentration and meeting various requirements across different applications. Moreover, numerous attempts have been undertaken to synthesize diverse NAGA-derived units through meticulous chemical structure regulation and fabricate corresponding H-bonding crosslinked supramolecular polymer materials. Despite this, the systematic clarification of the impact of chemical structures of side moieties on intermolecular associations and material performances remains lacking. The present review will focus on the design principle for synthesizing NAGA-derived H-bond side-chain units and provide an overview of the recent advancements in multiple H-bonds crosslinked PNAGA-derived supramolecular polymer materials, which can be categorized into three groups based on the chemical structure of H-bonds units: (1) monomers with solely cooperative H-bonds; (2) monomers with synergistic H-bonds and other physical interactions; and (3) diol chain extenders with cooperative H-bonds. The significance of subtle structural variations in these NAGA-derived units, enabling the fabrication of hydrogen-bonded supramolecular polymer materials with significantly diverse performances, will be emphasized. Moreover, the extensive applications of multiple H-bonds crosslinked supramolecular polymer materials will be elucidated.

Nowadays organosilicon luminescent materials are of increasing interest due to the variety of their synthetic or modification techniques and application fields. Ladder polyphenylsilsesquioxanes (L-PPSQ) are a unique class of organosilicon polymers, which can be ideal matrices for the luminescent composites due to their high thermal stability, optical transparency and mechanical strength. In this work, new mechanically strong, heat-resistant, transparent and sensitive to ammonia vapor luminescent composite films based on L-PPSQ have been obtained. As the source of Europium ions oligophenyleuropiumsiloxane was used, demonstrating perfect compatibility to the matrix due to the similar nature. To improve luminescent properties of the films, new organosilicon ligands were introduced into the composites and their influence on the properties of the materials was studied. Valuable properties of described composites may allow their further application as multifunctional coatings.

Developing hydroscopic actuators with simultaneous high elasticity, shape programmability and tunable actuating behaviors are highly desired but still challenging. In this study, we propose an orthogonal composite design to develop such a material. The developed composite elastomer comprises carboxyl group-grafted polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS-g-COOH) as the elastic substrate, and a synthesized azobenzene derivative as the functional filler (Azo12). By surface treatment using acidic and base solutions, the carboxyl groups on the surface can reversibly transform into carboxylate groups, which render the composite tunable hygroscopic actuating functionality. On another aspect, the added filler undergoes trans-to-cis isomerization when exposed to UV light irradiation, leading to liquefaction of the crystalline aggregates formed by Azo12 molecules. The liquefied Azo12 molecules can autonomously resotre their trans form and reform the crystalline structure. This reversible change in crystralline structure is utilized to realize the shape memory property, and 5 wt% of Azo12 addition is adequate for the composite to exhibit photo-responsive shape memory behavior without compromising much of the elasricity. The regualtion of external geometry by shape memory effect is effective in altering the actuating behavior. The proposed method can be extend to designing different composites with the demonstrated functionalities.

In this study, we synthesized a series of ABA-type vitrimers by crosslinking the short A moieties of precursors with a bifunctional crosslinker and evaporating the small molecular byproduct. The vitrimer samples thus prepared exhibit linear viscoelasticity dependent on the length of A moiety as well as the content of the crosslinks. When the average number of A monomers per end moiety m=1.1, the crosslinker can only extend the chain but not crosslink the chain. When m becomes 2.8 or higher, introducing a crosslinker first leads to the gelation, whereas excess in crosslinker molecules leads opening of the crosslinking sites and accordingly reentry into the sol regime. Surprisingly, a further increase in the length of the A moieties increases the relaxation time much weaker than the exponential increase seen for the physically crosslinked ABA-type ionomers. We attribute this difference to the distinct relaxation mechanisms: the relaxation of the vitrimer samples is based on relatively independent exchange reactions, which contrasts with the ABA-type ionomers that relax through the collective hopping of connected ionic groups from one ion aggregate to another.

Polyimides are a family of high-tech plastics that have irreplaceable applications in the fields of aerospace, defense, and opto-electronics, but polyimides are difficult to be reprocessed and recycled at the end of their service life, resulting in a significant waste of resources. Hence, it is of great significance to develop recyclable polyimides with comparable properties to the commercial products. Herein, we report a novel polymer-to-monomers chemically recyclable poly(imide-imine) (PtM-CR-PII) plastic, synthesized by cross-linking the amine-terminated aromatic bisimide monomer and the hexa-vanillin terminated cyclophosphazene monomer via dynamic imine bonds. The PtM-CR-PII plastic exhibits comparable mechanical and thermal properties as well as chemical stability to the commercial polyimides. The PtM-CR-PII plastic possesses a high Young’s modulus of ≈3.2 GPa and a tensile strength as high as ≈108 MPa, which also exhibits high thermal stability with a glass transition temperature of ≈220 °C. Moreover, the PtM-CR-PII plastic exhibits outstanding waterproofness, acid/alkali-resistance, and solvent-resistance, its appearance and mechanical properties can be well maintained after long-term soaking in water, highly concentrated acid and base, and various organic solvents. Furthermore, the cyclophosphazene moieties endow the PtM-CR-PII plastic with excellent flame retardancy. The PtM-CR-PII plastic exhibits the highest UL-94 flame-retarding rating of V-0 and a limiting oxygen index (LOI) value of 45.5%. Importantly, the PtM-CR-PII plastic can be depolymerized in an organic solvents-acid mixture medium at room temperature, allowing easy separation and recovery of both monomers in high purity. The recovered pure monomers can be used to regenerate new PtM-CR-PII plastics, enabling sustainable polymer-monomers-polymer circulation.