Polymer最新文献

Design of functional materials with tunable properties based on anionically-modified copolymer network of poly (N-isopropyl acrylamide-co-methacrylic acid) P(NIPA-co-MA) containing linear polyacrylamide and various amounts of Halloysite nanotubes (Hal) was presented using a facile route of solution casting. The organic/inorganic nanostructures based on thermo-responsive PNIPA were constructed to create hybrid materials via in situ polymerization with different Hal-loading and then used for the removal of cationic methylene blue (MB) dye from aqueous solutions. To achieve the desired mechanical property, the optimum composition of hybrids was determined following a simple and cost-effective synthesis procedure. In situ one-pot polymerization was promoted by semi-IPN formation, following a much simpler route than traditional preparation approaches for stable cross-linked hybrid formation. The swelling of hybrids decreased by 2.9-fold with loading of 5.40 % Hal, confirming the hydrogen bonding interactions between Hal and PAAm/P(NIPA-co-MA) network. The mechanical properties of Hal-doped hybrid gels showed an increase–decrease tendency with increase of Hal-content from 0.80 to 5.40 % (w/v) due to the high aspect ratio of Hal and strong secondary interactions between Hal and PAAm/P(NIPA-co-MA) chains. The effective cross-link density for Hal-doped hybrids was expressed by a cubic polynomial as a function of Hal concentration. Temperature-sensitive swelling results showed that the advantage of sustained release property of Hal can be combined with excellent controllability of PNIPA-based network. Adsorption results of MB onto Hal-doped hybrids bearing methacrylic acid moieties demonstrated their potential as efficient adsorbents for the removal of cationic dyes. A new route offered by the proposed procedure for design of hybrids containing “green” one-dimensional nanofillers creates an innovative perspective on robust hybrid structures for practical applications.

The structural evolution of high-crystallinity polyglycolide (PGA) during hot-stretching from 50 °C to 150 °C was investigated using synchrotron in-situ WAXD/SAXS techniques. The structural evolution during stretching at different temperatures can be divided into three stages. The stage preceding the yield point, the lamellar crystals undergo extensive slip due to shear forces. The crystallite size decreases by 43.9 % during stretching at 50 °C, while it only decreases by 23.8 % at 150 °C. In this stage, cavities with their long axes vertical to the stretching direction form between the lamellar stacks parallel to the stretching direction. Higher stretching temperatures are less favorable for the formation of these cavities. Stage from yield point to onset of strain hardening, some of the small crystals formed in the previous stage accumulate in the oblique direction. After reaching the critical strain, they reorient towards the stretching direction. This reorientation causes fragmentation and recrystallization, promoting the further development of cavities. Both the cavities and the recrystallized crystals align along the stretching direction. In the strain-hardening stage, new crystal formation occurs under stress, and higher temperatures favor the formation of highly oriented crystals. As a result, the crystallinity and crystal orientation of PGA at the end of stretching are positively correlated with the stretching temperature.

The entanglement disorder, highly polar groups and carbon-rich structure of conventional epoxy resins result in high dielectric constants and flammability, posing challenges to the development of high-frequency communications. Therefore, a silicone-containing active ester curing agent (FMAE) derived from magnolol was synthesized via a straightforward two-step process. And a thermosetting resin (FMAE/TGDDM) was then obtained by moisture self-cross-linking as well as curing epoxy N, N, N, N-tetraethoxypropyl-4, 4-diaminodiphenylmethane (TGDDM). The epoxy resin (MAE/TGDDM) cured by MAE that was not undergoing click chemistry was used for comparison. The results showed that the large volume of curing agents (31.86 Å × 14.98 Å × 9.03 Å for FMAE, 16.01 Å × 11.46 Å × 8.09 Å for MAE) and the absence of –OH enabled both resins to have excellent dielectric properties, especially FMAE/TGDDM, with a D_k of 2.78 and a D_f of 0.0066 at 10 MHz. Additionally, FMAE/TGDDM demonstrated favorable impact resistance (43.9 kJ/m²) and lower hygroscopicity (0.56%) than MAE/TGDDM, which due to the introduction of siloxane chain (Si% = 7.08%) and the increase of the crosslinking density (2302 mol/cm³ vs 6751 mol/cm³). Furthermore, the charring rate of FMAE/TGDDM was 39.1%, almost twice that of MAE/TGDDM, and the PHHR and THR were 201.2 W/g and 22.6 kJ/g, 103.9% and 67.7% lower than MAE/TGDDM, respectively, proving that the intrinsic flame retardancy of FMAE/TGDDM. Hence, this paper provides a strategy to synergistically address the limitations of TGDDM and conventional epoxy resins for impact resistance, dielectric properties and flame retardancy through a simple structural design.

In order to replace toxic fluorinated surfactants such as PFOA and GenX, herein we report a series of non-fluorinated surfactants (NFS) for the emulsion polymerization of fluorinated monomers. The surfactant is a statistic copolymer synthesized from free radical polymerization of poly(ethylene oxide) methacrylate (PEGMA) as hydrophilic monomer with methyl methacrylate (MMA) or tert-butyl methacrylate (TBMA) as hydrophobic comonomer. With properly designed hydrophile lipophile balance (HLB), monomer ratio, and the length of PEG segments, the polymeric NFS form unimolecular micelles in water, which facilitates the emulsion polymerization of fluorinated monomers including vinyl difluoride (VDF) where the solid content of emulsion can be higher than 25 wt% without the occurrence of significant coagulation. The optimized loading ratio of NFS is as low as 88 ppm which is ten times lower than that of fluorinated surfactants. The results demonstrate that the statistic copolymers construct unimolecular micelles to be powerful NFS for the emulsion polymerization of fluorinated monomers.

Polyisoprene (PI) is a widely used polymer and constructing a systematic coarse-grained (CG) PI model with the structural and thermodynamic consistency with the underlying atomic model over a wide range of thermodynamic conditions is very important for the predictive capability of CG model on overall properties of PI polymer materials and the establishment of their structure-property relationship. However, as the number of tunable CG potential parameters and target properties grows, traditional parameter tuning methods become impractical. In this work, we present a novel approach for determining the optimal CGPI non-bonded potential parameters by employing Particle Swarm Optimization as the calibrator with machine learning-based models trained using molecular dynamics data. The resulting CG model is further augmented with temperature factors through a multistate parameterization approach. This enhancement ensures the model's temperature transferability of structure and thermodynamics in a wide temperature of $150K\sim 750K$.

Since the physical and mechanical properties of semicrystalline polymers strongly depend on crystalline morphology, understanding the correlation between the crystallization kinetics and crystalline structure of polythene is beneficial for their rational processing and applications. In this study, united-atom (UA) molecular dynamics (MD) simulations were employed to elucidate the variations in crystalline structure, phase transition temperatures, and uniaxial tensile deformation among polyethylene (PE) with randomly oriented and flow-induced crystallization (FIC). The results showed that crystallization occurs in areas with low potential energy. For the FIC process, the entanglement parameter and interplanar spacing was less than for randomly oriented crystallization, and the crystallinity was higher. The relationship between the deformation and the crystallinity of PE with randomly oriented crystallization was expressed, which indicates that the crystalline structure promoted elongation at break of PE in tensile deformation. As PE was oriented to crystallize during the FIC process, the polymer stiffness is positively correlated with the deformation ratio of the PE model, so crystal conformation systems with higher deformation ratios produce higher ultimate stresses in tensile loading. From the visualization results, the crystalline phase was stable and does not easily transform into an amorphous phase during tensile loading. Additional results show that the fracture region of PE at tensile fracture tends to develop in the amorphous phase under tensile loading. Energy analysis showed that the elastic and yield regions were mainly dominated by intra-chain bonds, angles, and dihedral motion of PE, whereas interchain nonbonded interactions mainly dominated strain-hardening regions.

Despite the wide industrial application of poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether) (PFA) in semiconductor processing, its crystallization behavior has little been studied. In this work, three PFA resins with similar molecular weight but different comonomer content and distribution were synthetized. Then the non-isothermal crystallization kinetics and crystalline structures were studied by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction systematically. It is found that the incorporation of comonomers destroys the chain regularity and reduces the crystallizability of PFA thermodynamically, while the comonomer insertion improves the chain flexibility to accelerate the crystal growth dynamically. When the comonomer content of PFA is low, both the nucleation and growth rates are quite fast, which is favorable for the formation of spherulite. As the comonomer content increases or distribute uniformly in the chain, the nucleation rate declines notably and the side groups distort the crystal cell to increase the spacing of [100] plane. Moreover, two-dimensional growth mode is dominant to form bundle-like structure when crystallizing at slow cooling, where nucleation is suppressed by growth. But three-dimensional symmetrical spherulite can be activated and perfected at high cooling rate due to the initiation of substantial nucleation sites. This unique crystallization behavior is opposite to that of conventional polymers, providing a guidance for the polymerization and processing of PFA.

The limited anti-fatigue performance of self-healing polyurethane elastomers under high-strain conditions restricts their application in high-performance ionic skins. Herein, a polyurethane network (PU-DDN) synergistically reversibly crosslinked by dynamic thiourethane bonds and hydrogen bonds was synthesized successfully. This dual reversibly crosslinking strategy not only endowed the polyurethane network with an excellent fatigue resistance (showing a residual strain of only 63 % after 10 uninterrupted cyclic tensile tests at 400 % strains), but also imparted it with a high strength (6.12 MPa) and stretchability (611.42 %). Owing to the thermo-reversibility of dual dynamic networks, the damaged PU-DDN heated at 100 °C for 3h could fully restore its initial mechanical properties. Subsequently, transparent stretchable ionic skins were fabricated by mixing the PU-DDN with ionic liquids. A resulting highly-sensitive ionic skin (GF₁ = 1.25, GF₂ = 2.01) named PU-DDN/IL20 demonstrated exceptional durability, which could produce repeatable electrical signals even after 2000 cycles of stretching to an extensive deformation of 400 %. Meanwhile, it can also monitor human motions, showcasing its promising potential in the realm of intelligent wearable applications.

Coumarin-containing amphiphilic block copolymers with different compositions, as a new class of pH- and photo-responsive flocculants, were synthesized through reversible addition-fragmentation chain transfer polymerization of dimethyl aminoethyl methacrylate (DMAEMA), methyl methacrylate, and 7-acryloyloxy 4-methylcoumarin. Proton nuclear magnetic resonance spectroscopy was used to study the structure and composition of the copolymers. Zeta potential results show that the copolymers are applicable as amphoteric flocculants. The optimal flocculant concentration was calculated using the Jar analysis for kaolin flocculation, and the results show that the flocculation dependence on the flocculent concentration decreases with increasing its molecular weight. The dominance of charge neutralization in the flocculants with lower molecular weights and the dominance of adsorption bridging and hydrophobic association in the flocculants with higher molecular weights were indicated. These results are in agreement with the rheological data. To investigate the governing mechanism more precisely, the flocculation rate was calculated using turbidity measurements at different pH values over time. The highest final flocculation rate (99.25 %) corresponds to pH 4.5, which caused by the protonation of the amine groups of the DMAEMA repeating units. The dependence of settling rate on pH indicates the pH-dependent performance of the flocculants. Finally, fluorescence microscopy image of the flocculants shows its proper functioning of in the vicinity of kaolin, which has a promising industrial application.

A commercial recycled paperboard was double coated with poly (butylene adipate-co-terephthalate) (PBAT) films by using hot pressing aiming the production of a laminated material compatible with food packaging. The proposed new approach allowed to smooth the paperboard surface and to obtain a material with low oxygen permeability, low wettability, and excellent resistance to grease (kit value of 12). The observations by scanning electron microscopy (SEM) showed a homogeneous surface with a high degree of coverage, suggesting good compatibility of the PBAT with the cellulose fibers. Some of the mechanical properties of the PBAT-coated paperboard were also greatly improved, such as ply-bonding, bending resistance and bursting strength, which are important for packaging applications. Remarkably, it was possible to firmly bond two pieces of paperboard coated with PBAT by simply hot-pressing at an appropriate temperature. This method created a reinforced coated paperboard that showed high potential to be used in the production of laminated food packaging with different structures without the need of adhesives.