Post-Polymerization Heat Effect in the Production of Polyamide 6 by Bulk Quasiliving Anionic Ring-Opening Polymerization of ε-Caprolactam with Industrial Components: A Green Processing Technique

Bulk, solventless anionic ring-opening polymerization (AROP) of ε-caprolactam (CPL) with high yields, without side products and with short reaction times, initiated by caprolactamate-carbamoylcaprolactam initiating systems belong to green polymerization processes, leading to poly(ε-caprolactam) (Polyamide 6, PA6, Nylon 6). However, the effect of post-polymerization heat (i.e., slow, technically feasible cooling) on the fundamental characteristics of the resulting polymers such as yield and molecular weight distributions (MWDs) have not been revealed thus far. Significant post-polymerization effect was found by us in terms of both monomer conversions and MWDs by carrying out CPL polymerization with industrial components under conditions mimicking thermoplastic reaction transfer molding (T-RTM). Remarkably, higher monomer conversions and molecular weights (MWs) were obtained for Polyamide 6 samples prepared without quenching than that for the quenched polymers at the same reaction times. Independent of quenching or non-quenching, Mn of the resulting polymers as a function of conversion fell in the theoretical line of quasiliving AROP of CPL. At high monomer conversions, significant increase of the MW and broadening of the MWDs occurred, indicating pronounced chain–chain coupling. These findings have fundamental importance for designing processing conditions for in situ polymerization processes of ε-caprolactam by various techniques such as T-RTM, reaction injection molding (RIM), and other processing methods of Polyamide 6.

Elaboration of nanostructured polyurethane foams/OMMT using a twin-screw extruder in counter-rotating mode

In this work, a new elaboration method for nanostructured foam polyurethane/ organo-modified montmorillonite (PUR/OMMT) by in situ polymerization is proposed. A twin-screw extruder in the contra-rotation mode combined with reaction injection molding (RIM) as the polymerization process was used. The blended polyols, copolymer polyol (CPP) were included between the OMMT layers via the twin-screw extruder. Both the formulation of the PUR and the inter-foliar distance in the montmorillonite (MMT) were optimized. The effect of some parameters such as OMMT content and catalyst (triethylenediamine for PUR 3 and triethylenediamine+diamino-1,2 propane for PUR 4) was also investigated. The synthesized materials (OMMT, PUR and PUR/OMMT) were characterized by different methods, i.e., Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results of evaluation tests, such as flammability and the tensile for the PUR 3+OMMT foams revealed that the optimum properties were obtained for PUR 3+2 % OMMT. The PUR 4 foam showed better mechanical and flame- -retardant properties than the PUR 3 (r = ?NCO/?OH = 1.15) foam. However, the PUR 4 + 2 % OMMT formula exhibited the most delayed flame diffusion and pronounced rigidity.

LABORATORY-SCALE REACTION INJECTION MOLDING OF POLY(CAPROLACTONE) ELASTOMERS FOR RAPID PROTOTYPING OF STIMULI-RESPONSIVE THERMOSETS

ABSTRACT Semicrystalline polymer networks offer valuable shape-memory and shape-shifting properties; however, material processing and scale-up remain major challenges. A laboratory-scale reaction injection molding (RIM) apparatus and methodology are described to mold and cure urethane linked poly(caprolactone) networks from commercially available polyols and polyisocyanate. The highly customized RIM system is capable of making small shot sizes (∼39 g) at precise stoichiometric ratios and forming elastomers with low run-to-run variation of mechanical properties. Experiments conducted with a dye in one feed stream enable evaluation of mixing efficacy, and component mixing is substantially improved by recirculating reagents at higher pressures. Networks prepared with excess isocyanate exhibited higher modulus, which is most likely due to the formation of allophanates.

Mechanical properties of norbornene-based silane treated glass fiber reinforced polydicyclopentadiene composites manufactured by the S-RIM process

A lab scale structural reaction injection molding (S-RIM) piece of equipment was designed and used to fabricate glass fiber reinforced polydicyclopentadiene (p-DCPD) composites for three different fiber contents. In order to obtain information regarding the optimal process temperature (>80°C) and the curing time (<30 s), differential scanning calorimetry (DSC) was used to investigate the curing behavior of DCPD resin under isothermal conditions. Further, a norbornene-based silane treatment was used to improve the interfacial adhesion between the glass fibers and DCPD as confirmed by the micro-droplet pull-out test and scanning electron microscopy (SEM). Fabrication of glass fiber/p-DCPD composites with improved mechanical properties was carried out based on the optimized process conditions and surface treatment of glass fiber.