Polydiacetylenes

Polydiacetylenes
Author: D. Bloor
Publisher: Springer Science & Business Media
Total Pages: 413
Release: 2013-03-09
Genre: Science
ISBN: 9401727139

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The polydiacetylenes are a class of polymers that are attrac ting increasing attention worldwide. There are many reasons for this interest one of the most important being the availability of many polydiacetylenes as macroscopic, high quality, single crystals. This fact was first reported in the pioneering work of Prof. G. Hegner on the solid-state polymerization of disub stituted diacetylenes in the late 1960s. Since then studies of the polymerization process and the properties of monomers and polymers have advanced understanding of solid-state reactivity and the physiCS of quasi-one-dimensional materials. More recently work on soluble polydiacetylenes, gels and films has been of interest for both academic and technological reasons. Progress in this area has required a combination of research disciplines ranging from synthetic organic chemistry to solid state physics. The interdisciplinary effort required for success ful research in polydiacetylenes was reflected in the mix of chemists, physicists and materials scientists who attended the Workshop. The emerging potential for commercial applications of polydiacetylenes was also evident in the nearly equal partici pation of academic and industrial/government scientists. The WOrkshop was the first major international meeting to focus solely on polydiacetylenes. It provided a forum in which problems of mutual interest could be discussed by scientists with diverse backgrounds and interests. It also satisfied the need for a review of the science of these materials at a time when this basic understanding is leading to technological applications.

Synthesis and Characterization of Ionically Crosslinked Networks

Synthesis and Characterization of Ionically Crosslinked Networks
Author: Qinyuan Chai
Publisher:
Total Pages: 77
Release: 2013
Genre: Chemical bonds
ISBN:

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The overall goal of this thesis was to investigate the synthesis and characterization of elastomeric polymer networks crosslinked by ion-pairs. To generate these networks, cationic polyacrylate ionomers with styrene sulfonate counter-ions were synthesized. These polymers were used to generate ionically crosslinked networks by copolymerization of the pedant vinyl ionomers with acrylate monomer. These ionically crosslinked elastomers swelled in organic solvent like covalently crosslinked elastomers, but could be dissolved and re-gelled by dissociating and re-associating the ionic bonds by double ion-exchange reactions under acidic and basic conditions. Uniaxial tensile testing and oscillatory shear rheology were used to characterize the mechanical properties of the materials and compared to covalently crosslinked control samples. In contrast to the covalently crosslinked polymers, the ionically crosslinked samples showed strong property dependence on temperature and level of strain. At room temperature, the ionically crosslinked polymer had similar properties with a covalently crosslinked elastomer. As the temperature was increased above 100°C, the fluid-like property became more and more obvious due to the rearrangement of the ionic bonds. In addition, under load the ionically crosslinked polymer also exhibited flow. This mechano-chemical response of the materials to reconfigure the network under thermo-mechanical load should provide opportunities for developing new processable and self-healing elastomers using ionic interactions.

Independent and Interconnected Interpenetrating Polymer Network Formation In Dual-Cure Thermoset Resins

Independent and Interconnected Interpenetrating Polymer Network Formation In Dual-Cure Thermoset Resins
Author: Jessica Kopatz
Publisher:
Total Pages:
Release: 2021
Genre:
ISBN:

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Thermoset polymers are of interest for many structural applications due to their mechanical, thermal, and chemical resiliency in comparison to thermoplastic polymers. However, utilizing thermosets in the realm of additive manufacturing is still a developing field, especially when using viscous thermosets where long cure times can limit the shape retention of 3D printed parts. There has been increased interest in the development of direct-ink-write (DIW) methods for thermoset resins in the last several years. The approaches generally fall into two categories; dual-cure systems or filled resins. Dual-cure resins are comprised of multiple thermoset polymers that are cured using different stimuli or variations of the same stimuli (i.e. temperatures, wavelengths, etc.). Common dual-cure thermoset resins consist of a photo-curable acrylate and a thermally-curable epoxy. For sequential dual-cure systems, the photo-cure mechanism can be rapidly completed immediately after extrusion from the print tip in order to lock-in the desired structure, while the sequential thermal cure forms the epoxy network and enhances the composite properties. Sequential curing of the resin, via UV exposure followed by thermal exposure, creates interpenetrating polymer networks (IPNs), which can enhance the overall thermomechanical properties compared to either parent material. IPNs consist of two or more networks that are interwoven on a molecular scale. Though the networks are not covalently bound to each other, they cannot be separated unless chemical bonds are broken. Independent IPNs exist where there are two separate but interwoven networks, while interconnected IPNs form by the addition of a heterobifunctional monomer that links the two networks together. Interconnected IPNs are expected to result in the best properties due to the tethering of the two otherwise separate networks. The filled resins approach to the DIW of thermosets generally require the material to possess high zero-shear viscosity, shear thinning behavior, and controlled curing. High zero-shear viscosity permits shape retention post-extrusion, while shear thinning enables the fluid to flow easily through the print head. To enable shear thinning, fillers such as clay or silica are added, where the filler is usually modified to enable better dispersion within the polymer matrix. Not only does the addition of inorganic fillers alter the rheology and printability of the resin, the fillers can also impact the thermomechanical properties of the composite. This thesis describes the influence of resin composition on the printability and 'green strength' of printed parts. After the sequential thermal cure in the dual-cure system, the impact of acrylate network formation on the evolution and formation of independent IPNs was investigated. Moving to a more simplified dual-cure acrylate-epoxy resin system, the impact of acrylate-functionalized and epoxy-functionalized filler particles as network crosslinkers was explored. Finally, the influence of heterobifunctional acrylate-epoxy hybrid monomers with differing backbones on the formation of interconnected IPNs was investigated.

Effect of the Reaction Sequence of an Epoxy Polybutadiene Acrylate Interpenetrating Polymer Network Properties

Effect of the Reaction Sequence of an Epoxy Polybutadiene Acrylate Interpenetrating Polymer Network Properties
Author: Kathryn Grace Bearden
Publisher:
Total Pages: 30
Release: 2012
Genre:
ISBN: 9781267433640

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Interpenetrating polymer networks (IPNs), where polymer chains mechanically entangle during network formation, are of interest for their unique properties. The reaction sequence of a DGEBF epoxy/polybutadiene-dimethacrylate simultaneous IPN system was varied with differing catalysts to observe the correlation between reaction steps and physical properties. When the acrylate components were reacted first an IPN with two glass transitions and discrete phase separation was observed via scanning electron microscopy (SEM). When all components were reacted in parallel, two glass transitions were also observed but the morphology presented a single phase or a visible macro phase seperation. The IPN showed an increase in fracture toughness but a decrease in tensile strength compared to the single phase system and an epoxy control. Varying the amounts of polybutadiene-dimethacrylate in relation to the epoxy also showed a limit to the toughening effect.