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Abstract Many commodity plastics, such as thermoplastic polyurethanes (PUs), require reinforcement for use as commercial products. Cellulose nanocrystals (CNCs) offer a “green” and scalable approach to polymer reinforcement as they are exceptionally stiff, recyclable, and abundant. Unfortunately, achieving efficient CNC reinforcement of PUs with industrial melt processing techniques is difficult, mostly due to the incompatibility of the hydrophobic PU with hydrophilic CNCs, limiting their dispersion. Here, a hydrophilic PU is synthesized to achieve strong reinforcement in melt‐processed nanocomposite fibers using filter paper‐sourced CNCs. The melt‐spun fibers, exhibiting smooth surfaces even at high CNC loading (up to 25 wt%) indicating good CNC dispersion, are bench‐marked against solvent‐cast films—solvent processing is not scalable but disperses CNCs well and produces strong CNC reinforcement. Mechanical analysis shows the CNC addition stiffens both nanocomposite films and fibers. The stress and strain at break, however, are not significantly affected in films, whereas adding CNCs to fibers increases the stress‐at‐break while reducing the strain‐at‐break. Compared to earlier studies employing a hydrophobic (and stiffer) PU, CNC addition to a hydrophilic PU substantially increases the fiber stiffness and strength. This work therefore suggests that rendering thermoplastics more hydrophilic might pave the way for “greener” polymer composite products using CNCs.
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Design, synthesis, and characterization of vinyl-addition polynorbornenes with tunable thermal properties
Unfunctionalized vinyl-addition polynorbornene (VAPNB) possesses many outstanding properties such as high thermal, chemical, and oxidative stability. These features make VAPNB a promising candidate for many engineering applications. However, VAPNB has a small service window between its glass transition temperature ( T g ) and decomposition temperature ( T d ), and it cannot be readily processed in a melt state. In this work, we demonstrate that the service window of VAPNBs can be tailored through the use of norbornene monomers bearing alkyl, aryl, and aryl ether substituents. The vinyl addition homopolymerization and copolymerization of these functionalized norbornyl-based monomers yielded VAPNBs with high T ′ g s (>150 °C) and large service windows ( T d – T g > 100 °C), which are comparable to other commercial engineering thermoplastics. To further establish the feasibility of melt processing, a functionalized VAPNB material with T g = 209 °C and a service window of 170 °C was successfully extruded and molded into bars. Subsequent characterization of the bars by dynamic mechanical analysis (DMA), nuclear magnetic resonance spectroscopy (NMR), and gel permeation chromatography (GPC) revealed only minor signs of polymer degradation. These studies suggest that substituted VAPNBs could be developed into a new class of engineering thermoplastics that is compatible with workhorse melt processing techniques such as extrusion and injection molding, as well as emerging techniques such as extrusion-based 3D printing.
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- Award ID(s):
- 1827474
- PAR ID:
- 10309626
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 12
- Issue:
- 40
- ISSN:
- 1759-9954
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1PY01050F
