Polysiloxanes represent a unique class of synthetic polymers, employing a completely inorganic backbone structure comprised of repeating –(Si–O)n– 'siloxane' main chain linkages. This results in an assortment of diverse properties exclusive to the siloxane bond that clearly distinguish them from the –(C–C)n– backbone of purely organic polymers.
Previous work has elucidated a methodology for fabricating flexible and elastic crosslinked poly(dimethyl siloxane) (PDMS) constructs with high Mc through a simultaneous crosslinking and chain-extension methodology. However, these constructs suffer the poor mechanical properties typical of lower molecular weight crosslinked siloxanes (e.g. modulus, tear strength, and strain at break). Filled PDMS networks represent another important class of elastomers in which fillers, namely silica and siloxane-based fillers, impart improved mechanical properties to otherwise weak PDMS networks. This work demonstrates that proper silicon-based reinforcing agent selection (e.g. siloxane-based MQ copolymer nanoparticles) and incorporation provides a synergistic enhancement to mechanical properties, whilst maintaining a low viscosity liquid composition, at high loading content, without the use of co-solvents or heating. Rheological analysis evaluates the viscosity while photorheology and photocalorimetry measurements evaluate rate and extent of curing of the various MQ-loaded formulations, demonstrating theoretical printability up to 40 wt% MQ copolymer nanoparticle incorporation. Dynamic mechanical analysis (DMA) and tensile testing evaluated thermomechanical and mechanical properties of the cured nanocomposites as a function of MQ loading content, demonstrating a 3-fold increase in ultimate stress at 50 wt% MQ copolymer nanoparticle incorporation. VP AM of the 40 wt% MQ-loaded, photo-active PDMS formulation demonstrates facile amenability of photo-active PDMS formulations with high MQ-loading content to 3D printing processes with promising results.
PDMS polyureas represent an important class of elastomers with unique properties derived from the synergy between the nonpolar nature, unusual flexibility, and low glass transition temperature (Tg) afforded by the backbone siloxane linkages (-Si-O)n- of PDMS and the exceptional hydrogen bond ordering and strength evoked by the bidentate hydrogen bonding of urea. The work herein presents an improved melt polycondensation synthetic methodology, which strategically harnesses the spontaneous pyrolytic degradation of urea to afford a series of PDMS polyureas via reactions at high temperatures in the presence of telechelic amine-terminated oligomeric poly(dimethyl siloxane) (PDMS1.6k-NH2) and optional 1,3-bis(3-aminopropyl)tetramethyldisiloxane (BATS) chain extender. This melt polycondensation approach uniquely circumvents the accustomed prerequisite of isocyanate monomer, solvent, and metal catalysts to afford isocyanate-free PDMS polyureas using bio-derived urea with the only reaction byproduct being ammonia, a fundamental raw ingredient for agricultural and industrial products.
As professed above, reinforcement of polysiloxane materials is ascertained via the incorporation of reinforcing fillers or nanoparticles (typically fumed silica) or blocky or segmented development of polymer chains eliciting microphase separation, in order to cajole the elongation potential of polysiloxanes. Herein, a facile approach is detailed towards the synergistic fortification of PDMS-based materials through a collaborative effort between both primary methods of polysiloxane reinforcement. A novel one-pot methodology towards the facile, in situ incorporation of siloxane-based MQ copolymer nanoparticles into segmented PDMS polyureas to afford MQ-loaded thermoplastic and thermoplastic elastomer PDMS polyureas is detailed. The isocyanate-free melt polycondensation achieves visible melt dispersibility of MQ copolymer nanoparticles (good optical clarity) and affords segmented PDMS polyureas while in the presence of MQ nanoparticles, up to 40 wt% MQ, avoiding post-polymerization solvent based mixing, the only other reported alternative. Incorporation of MQ copolymer nanoparticles into segmented PDMS polyureas provides significant enhancements to modulus and ultimate stress properties: results resemble traditional filler effects and are contrary to previous studies and works discussed in Chapter 2 implementing MQ copolymer nanoparticles into chemically-crosslinked PDMS networks. In situ MQ-loaded, isocyanate-free, segmented PDMS polyureas remain compression moldable, affording transparent, free-standing films. / Master of Science / Polysiloxanes, also referred to as 'silicones' encompass a unique and important class of polymers harboring an inorganic backbone. Polysiloxanes, especially poly(dimethyl siloxane) (PDMS) the flagship polymer of the family, observe widespread utilization throughout industry and academia thanks to a plethora of desirable properties such as their incredible elongation potential, stability to irradiation, and facile chemical tunability. A major complication with the utilization of polysiloxanes for mechanical purposes is their poor resistance to defect propagation and material failure. As a result polysiloxane materials ubiquitously observe reinforcement in some fashion: reinforcement is achieved either through the physical or chemical incorporation of a reinforcing agent, such as fumed silica, or through the implementation of a chemical functionality that facilitates reinforcement via phase separation and strong associative properties, such as hydrogen bonding. This research tackles polysiloxane reinforcement via both of these strategies.
Facile chemical modification permits the construction PDMS polymer chains that incorporate hydrogen bonding motifs, which phase separate to afford hydrogen bond-reinforced phases that instill vast improvements to elastic behavior, mechanical and elongation properties, and upper-use temperature. Novel nanocomposite formulation through the incorporation of MQ nanoparticles (which observe widespread usage in cosmetics) facilitate further routes toward improved mechanical and elongation properties.
Furthermore, with growing interest in additive manufacturing strategies, which permit the construction of complex geometries via an additive approach (as opposed to conventional manufacturing processes, which require subtractive approaches and are limited in geometric complexity), great interest lies in the capability to additively manufacture polysiloxane-based materials. This work also illustrates the development of an MQ-reinforced polysiloxane system that is amenable to conventional vat photopolymerization additive manufacturing: chemical modification of PDMS polymer chains permits the installation of UV-activatable crosslinking motifs, allowing solid geometries to be constructed from a liquid precursor formulation.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/100134 |
| Date | 01 October 2020 |
| Creators | Cashman, Mark Francis |
| Contributors | Chemistry, Long, Timothy E., Williams, Christopher B., Bortner, Michael J. |
| Publisher | Virginia Tech |
| Source Sets | Virginia Tech Theses and Dissertation |
| Detected Language | English |
| Type | Thesis |
| Format | ETD, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
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