Search Results (10)

Cyclohexane-containing semi-aromatic polyamides (c-SaPA) exhibit excellent comprehensive properties. Existing studies predominantly focus on synthesis and modification, while fundamental investigations into pyrolysis mechanisms remain limited, which restricts the development of advanced materials for high-performance applications such as automotive and energy systems. This study employs Reactive Force Field Molecular Dynamics (ReaxFF-MD) simulations to establish a pyrolysis model for poly(terephthaloyl-hexahydro-m-xylylenediamine) (PHXDT), systematically probing its pyrolysis kinetics and evolutionary pathways under elevated temperatures. The simulation results reveal an activation energy of 107.55 kJ/mol and a pre-exponential factor of 9.64 × 10¹³ s⁻¹ for the pyrolysis process. The primary decomposition pathway involves three distinct stages. The first is initial backbone scission generating macromolecular fragments, followed by secondary fragmentation that preferentially occurs at short-chain hydrocarbon formation sites alongside radical recombination. Ultimately, the process progresses to deep dehydrogenation, carbonization, and heteroatom elimination through sequential reaction steps. Mechanistic analysis identifies multi-pathway pyrolysis involving carboxyl/amide bond cleavage and radical-mediated transformations (N-C-O, C-C-O, OH· and H·), yielding primary products including H₂, CO, H₂O, CH₃N, C₂H₂, and C₂H₄. Crucially, the cyclohexane structure demonstrates preferential participation in dehydrogenation and hydrogen transfer reactions due to its conformational dynamic instability and low bond dissociation energy, significantly accelerating the rapid generation of small molecules like H₂. Full article

The development of thermo-responsive shape-memory polymers has attracted attention due to their ability to undergo reversible deformations based on temperature changes. Vegetable oils are confirmed to be an excellent biorenewable source of starting materials for the synthesis of polymers. Therefore, the objective of this research was to synthesize thermo-responsive shape-memory polymers based on vegetable oils by using the dual-curing technique and obtaining polymers with tailorable properties. Acrylated epoxidized soybean oil and two epoxidized vegetable oils, linseed oil and camelina oil, were chosen for dual curing with m-xylylenediamine. Rheological tests were used to analyze the curing kinetics of systems undergoing radical photopolymerization, thermal cationic polymerization, and dual-curing processes. The rheological, mechanical, and thermal characteristics of the polymers were enhanced by the second curing stage. Dual-cured vegetable oil-based polymers had shape-memory properties with a recovery ratio of 100%, making them suitable for a variety of applications, including electronics, biomedical devices, and robotics. Full article

Structural adhesion at high temperature has been a challenge for organic adhesives, and the commercially available adhesives that can work at a temperature above 150 °C is rather limited. Herein, two novel polymers were designed and synthesized via facile strategy, which involves polymerization between melamine (M) and M–Xylylenediamine (X), as well as copolymerization of MX and urea (U). With well-balanced rigid-flexible structures, the obtained MX and MXU resins were proved to be outstanding structural adhesives at a wide range temperature of −196~200 °C. They provided room-temperature bonding strength of 13~27 MPa for various substrates, steel bonding strength of 17~18 MPa at cryogenic temperature (−196 °C), and 15~17 MPa at 150 °C. Remarkably, high bonding strength of 10~11 MPa was retained even at 200 °C. Such superior performances were attributed to a high content of aromatic units, which leads to high glass transition temperature (T_g) up to ~179 °C, as well as the structural flexibility endowed by the dispersed rotatable methylene linkages. Full article

Polyethylene glycol 1000 (PEG1000) and epoxy resin E20 were used to synthesize the E20/PEG1000 polymer (EP1K), which was later transformed into a self-emulsifying water-based epoxy curing agent by reacting with m-Xylylenediamine (MXDA). The effects of molecular weight, the molar ratio of the raw materials, the catalyst dosage, and the different co-solvents on the properties of the prepared curing agent were systematically explored. The infrared absorption spectra of E20, EP1K, and the water-based epoxy curing agent were compared and analyzed. The coating properties of the waterborne epoxy varnish, which was based on water-based epoxy curing agents to emulsify and cure the resin E44, were systematically tested. The results demonstrated that with a molar ratio of 1:1:4 of PEG1000, E20, and MXDA, the boron trifluoride etherate (BF₃·Et₂O) as catalyst accounts for 0.3% of the total mass of E20 and PEG1000, and an applicable period of 3 h for the prepared varnish, the anti-corrosion performance, and mechanical properties of the coatings were excellent. Full article

The effect of doping the bisphenol A diglycidyl ether (DGEBA)/m-xylylenediamine (mXDA) system with gold nanoparticles (AuNP) has been studied with differential scanning calorimetry (DSC), thermogravimetric analysis, dynamic mechanical analysis (DMA), and dielectric analysis (DEA). The evolved heat (ΔH_t), the glass transition temperature (T_g), and the associated activation energies of this relaxation process have been determined. Below a certain concentration of AuNPs (=8.5%, in mg AuNP/g epoxy matrix), T_g decreases linearly with the concentration of AuNPs, but above it, T_g is not affected. The degree of conversion α of this epoxy system was analyzed by the semiempirical Kamal’s model, evidencing that diffusion correction is required at high values of α. Activation energy values suggest that AuNPs can cause some impediments at the beginning of the crosslinking process (n-order mechanism). The slight difference between the initial decomposition temperature, as well as the temperature for which the degradation rate is at a maximum, for both systems can be accepted to be within experimental error. Mechanical properties (tension, compression, and bending tests) are not affected by the presence of AuNPs. Dielectric measurements show the existence of a second T_g at high temperatures, which was analyzed using the Tsagarapoulos and Eisenberg model of the mobility restrictions of network chains bound to the filler. Full article

Poly(hydroxyurethane)s (PHU) are alternatives for conventional polyurethanes due to the use of bis-cyclic dicarbonates and diamines instead of harmful and toxic isocyanates. However, the surface properties of poly(hydroxyurethane)s are not well known. In this work, we focus on the analysis of the surface properties of poly(hydroxyurethane) coatings. Poly(hydroxyurethane)s were obtained by a catalyst-free method from commercially available carbonated diglycidyl ether of bisphenol A (Epidian 6 epoxy resins) and various diamines: ethylenediamine, trimethylenediamine, putrescine, hexamethylenediamine, 2,2,4(2,4,4)-trimethyl-1,6-hexanediamine, m-xylylenediamine, 1,8-diamino-3,6-dioxaoctane, 4,7,10-trioxa-1,13-tridecanediamine, and isophorone diamine, using a non-isocyanate route. The structures of the obtained polymers were confirmed by FT-IR, ¹H NMR and ¹³C NMR spectroscopy, and thermogravimetric (TGA) and differential scanning calorimetry (DSC) analyses were performed. The rheological characteristic of the obtained polymers is presented. The static contact angles of water, diidomethane, and formamide, deposited on PHU coatings, were measured. From the measured contact angles, the surface free energy was calculated using two different approaches: Owens–Wendt and van Oss–Chaudhury–Good. Moreover, the wetting envelopes of PHU coatings were plotted, which enables the prediction of the wetting effect of various solvents. The results show that in the investigated coatings, a mainly dispersive interaction occurs. Full article

In order to synthesize a new kind of buoyancy material with high-strength, low-density and low-water-absorption and to study the curing reaction of tetraglycidylamine epoxy resin with an aromatic amine curing agent, the non-isothermal differential scanning calorimeter (DSC) method is used to calculate the curing kinetics parameters of N,N,N′,N′-tetraepoxypropyl-4,4′-diaminodiphenylmethane epoxy resin (AG-80) and the m-xylylenediamine (m-XDA) curing process. Further, buoyancy materials with different volume fractions of hollow glass microsphere (HGM) compounded with a AG-80 epoxy resin matrix were prepared and characterized. The curing kinetics calculation results show that, for the curing reaction of the AG-80/m-XDA system, the apparent activation energy increases with the conversion rates increasing and the reaction model is the Jander equation (three-dimensional diffusion, 3D, n = 1/2). The experimental results show that the density, compressive strength, saturated water absorption and water absorption rate of the composite with 55 v % HGM are 0.668 g·cm⁻³, 107.07 MPa, 0.17% and 0.025 h^−1/2, respectively. This kind of composite can probably be used as a deep-sea buoyancy material. Full article

Buoyancy material is a type of low-density and high-strength composite material which can provide sufficient buoyancy with deep submersibles. A new buoyancy material with N,N,N′,N′-tetraepoxypropyl-4,4′-diaminodiphenylmethane epoxy resin (AG-80) and m-xylylenediamine (m-XDA) curing agent as matrix and hollow glass microsphere (HGM) as the filler is prepared. The temperature and time of the curing process were determined by the calculations of thermal analysis kinetics (TAK) through differential scanning calorimetry (DSC) analysis. The results show that the better mass ratio of AG-80 with m-XDA is 100/26. Combined TAK calculations and experimental results lead to the following curing process: pre-curing at 75 °C for 2 h, curing at 90 °C for 2 h, and post-curing at 100 °C for 2 h. The bulk density, compressive strength, and saturated water absorption of AG-80 epoxy resin-based buoyancy material were 0.729 g/cm³, 108.78 MPa, and 1.23%, respectively. Moreover, this type of buoyancy material can resist the temperature of 250 °C. Full article

The successful synthesis of chiral amines from ketones using ω-transaminases has been shown in many cases in the last two decades. In contrast, the amination of β-keto acids is a special and relatively new challenge, as they decompose easily in aqueous solution. To avoid this, transamination of the more stable β-keto esters would be an interesting alternative. For this reason, ω-transaminases were tested in this study, which enabled the transamination of the β-keto ester substrate ethyl benzoylacetate. Therefore, a ω-transaminase library was screened using a coloring o-xylylenediamine assay. The ω-transaminase mutants 3FCR_4M and ATA117 11Rd show great potential for further engineering experiments aiming at the synthesis of chiral (S)- and (R)-β-phenylalanine esters. This alternative approach resulted in the conversion of 32% and 13% for the (S)- and (R)-enantiomer, respectively. Furthermore, the (S)-β-phenylalanine ethyl ester was isolated by performing a semi-preparative synthesis. Full article

Spectroscopic, viscometric, and molecular docking analysis of binding of cationic bis-porphyrins linked with p- or m-xylylenediamine (H₂pXy and H₂mXy) and their zinc(II) complexes (ZnpXy and ZnmXy) to duplex DNA are described. H₂pXy and H₂mXy bound to calf thymus DNA (CTDNA) stronger than unichromophoric H₂TMPyP, and showed exciton-type induced circular dichroism spectra of their Soret bands. The H₂TMPyP-like units of the metal-free bis-porphyrins did not intercalate into CTDNA, and thus the binding mode is outside binding with intramolecular stacking. ZnpXy showed favorable binding to A·T over G·C region, and should lie in the major groove of A·T region. Full article