Unique Method for Facile Postsynthetic Modification of Nonisocyanate Polyurethanes.

Nonisocyanate polyurethanes (NIPUs) are broadly investigated as a potential replacement for conventional polyurethanes (PUs) to eliminate the use of toxic isocyanates and reduce occupational hazards. One of the most popular approaches to NIPU synthesis is the polyaddition of cyclic bis(carbonate)s and diamines to form poly(hydroxyurethane)s (PHUs). However, such PHUs are highly hydrophilic due to the presence of two hydroxyl groups per repeat unit, and the resulting moisture absorption significantly degrades their thermomechanical performance and physical stability upon exposure to humidity, thus limiting their utility. Here, we introduce a simple and scalable approach for the modification of PHUs to increase hydrophobicity and adjust their properties. The proposed reaction between aldehydes and appropriately spaced hydroxyl groups in the polymer backbone resulted in high degrees of modification (up to 84%) and up to 3-fold reductions in water uptake at 85% RH. Furthermore, the use of aromatic aldehydes in particular enabled the retention of mechanical properties over a wide range of humidity levels, resulting in performance comparable to conventional PUs. Finally, we note that this approach is not limited to reducing moisture sensitivity alone and provides ample opportunities for imparting a broad range of novel properties to PHUs through an appropriate selection of functional aldehydes.

On the Addition of Multifunctional Methacrylate Monomers to an Acrylic-Based Infusible Resin for the Weldability of Acrylic-Based Glass Fibre Composites.

The melt strength of Elium® acrylic resin is an important factor to ensure limited fluid flow during welding. To provide Elium® with a suitable melt strength via a slight crosslink, this study examines the effect of two dimethacrylates, namely butanediol-di-methacrylate (BDDMA) and tricyclo-decane-dimethanol-di-methacrylate (TCDDMDA), on the weldability of acrylic-based glass fibre composites. The resin system impregnating a five-layer woven glass preform is a mixture of Elium® acrylic resin, an initiator, and each of the multifunctional methacrylate monomers in the range of 0 to 2 parts per hundred resin (phr). Composite plates are manufactured by vacuum infusion (VI) at an ambient temperature and welded by using the infrared (IR) welding technique. The mechanical thermal analysis of the composites containing multifunctional methacrylate monomers higher than 0.25 phr shows a very little strain for the temperature range of 50 °C to 220 °C. The quantity of 0.25 phr of both of the multifunctional methacrylate monomers in the Elium® matrix improves the maximum bound shear strength of the weld by 50% compared to those compositions without the multifunctional methacrylate monomers.

On the Hot-Plate Welding of Reactively Compatibilized Acrylic-Based Composites/Polyamide (PA)-12.

Joining of dissimilar thermoplastics and their composites is a challenge for thermal welding techniques due to different melting points. Reactive welding with an auxiliary functional material can offer the clear opportunities to develop joining processes due to robustness to joining dissimilar thermoplastic polymers and their composites. The current study employed reactive compatibilization to offer the possibility of joining an acrylic-based glass fiber composite to polyamide (PA)-12 by applying a hot-tool welding technique. For this purpose, composite plates are fabricated by a typical vacuum infusion and thin layer thermoplastic films are formed by a thermostamping of PA12 granules. Subsequently, the reactive welding of the interposed PA12 sheet and Elium®-GMA-Glass composite is conducted by hot-plate welding. A glycidyl methacrylate (GMA) as a compatibilizing agent is copolymerized with methyl methacrylate Elium® resin. During the hot-tool welding process of dissimilar thermoplastic material, GMA can react with the polyamide end groups. The heat distribution at the Elium® GMA/PA-12 interface is responsible for obtaining a strong joint. This study focuses on the functionality of the compatibilizer on the welding of acrylic-based composites with polyamide (PA)-12 while varying the assembly temperature. The flatwise tensile test proved the effectiveness of GMA on the interface bounding. The excellent bounding incompatible polymers Elium® resin (PMMA) and PA12 was achieved at 200 °C.

Effect of the structural features of biobased linear polyester plasticizers on the crystallization of polylactides.

This work presents, for the first time, a detailed report on how the nucleation and crystallization of polylactide (PLLA) are affected by biobased aliphatic polyesters plasticizers. Three biobased polyesters were synthesized via solvent-free two-stage melt polycondensation of adipic acid (AdA) with three different biobased aliphatic diols and used as plasticizers for poly (L-lactic acid) (PLLA). The molecular structure of the synthesized polyesters was proved using 1H NMR, 13C NMR and Fourier transform infrared (FTIR) spectroscopy. PLLA/AdA-based blends containing 10 wt% of the polyester plasticizers were studied by tensile tests, dynamic mechanical analysis (DMA), wide-angle x-ray scattering (WAXS), differential scanning calorimetry (DSC) and polarized light optical microscopy (PLOM). Adding the plasticizers to PLLA decreased Tg by up to 11 °C and significantly increased the elongation at break by about 8 times compared with neat PLLA. The addition of 10 wt% of any AdA-based plasticizer to PLLA increases the nucleation rate from the glassy state by around 50-110 % depending on the plasticizer. The overall crystallization rate from the glassy state was 2-3 times faster for the plasticized PLLAs than neat PLLA. These results are a consequence of the lower energy barrier for both nucleation and growth processes. The incorporation of AdA-based linear polyesters had an incremental impact on the crystal growth rate (or secondary nucleation) of PLLA spherulites from the melt and glassy states. In conclusion, the AdA-based aliphatic polyesters allowed to enhance PLLA crystallization rates and showed interesting potential for the formulation of fully biobased PLLA blends.

Fused Filament Fabrication of Polymers and Continuous Fiber-Reinforced Polymer Composites: Advances in Structure Optimization and Health Monitoring.

3D printed neat thermoplastic polymers (TPs) and continuous fiber-reinforced thermoplastic composites (CFRTPCs) by fused filament fabrication (FFF) are becoming attractive materials for numerous applications. However, the structure of these materials exhibits interfaces at different scales, engendering non-optimal mechanical properties. The first part of the review presents a description of these interfaces and highlights the different strategies to improve interfacial bonding. The actual knowledge on the structural aspects of the thermoplastic matrix is also summarized in this contribution with a focus on crystallization and orientation. The research to be tackled to further improve the structural properties of the 3D printed materials is identified. The second part of the review provides an overview of structural health monitoring technologies relying on the use of fiber Bragg grating sensors, strain gauge sensors and self-sensing. After a brief discussion on these three technologies, the needed research to further stimulate the development of FFF is identified. Finally, in the third part of this contribution the technology landscape of FFF processes for CFRTPCs is provided, including the future trends.

Plasticization of Polylactide with Myrcene and Limonene as Bio-Based Plasticizers: Conventional vs. Reactive Extrusion.

Polylactide (PLA) was blended by conventional and reactive extrusion with limonene (LM) or myrcene (My) as bio-based plasticizers. As-processed blends were carefully analyzed by a multiscale and multidisciplinary approach to tentatively determine their chemical structure, microstructure, thermal properties, tensile and impact behaviors, and hydrothermal stability. The main results indicated that LM and My were efficient plasticizers for PLA, since compared to neat PLA, the glass transition temperature was reduced, the ultimate tensile strain was increased, and the impact strength was increased, independently of the type of extrusion. The addition of a free radical initiator during the extrusion of PLA/LM was beneficial for the mechanical properties. Indeed, the probable formation of local branched/crosslinked regions in the PLA matrix enhanced the matrix crystallinity, the tensile yield stress, and the tensile ultimate stress compared to the non-reactive blend PLA/LM, while the other properties were retained. For PLA/My blends, reactive extrusion was detrimental for the mechanical properties since My polymerization was accelerated resulting in a drop of the tensile ultimate strain and impact strength, and an increase of the glass transition temperature. Indeed, large inclusions of polymerized My were formed, decreasing the available content of My for the plasticization and enhancing cavitation from inclusion-matrix debonding.