Exploration of the versatility of ring opening metathesis polymerization: an approach for gaining access to low density polymeric aerogels

Metal cation‐based anion exchange membranes (AEMs) are a unique class of materials that have shown potential to be highly stable AEMs with competitive conductivities. Here, we expand upon previous work to report the synthesis of crosslinked nickel cation‐based AEMs formed using the thiol–ene reaction. These thiol–ene‐based samples were first characterized for their morphology, both with and without nickel cations, where the nickel‐containing membranes demonstrated a disordered scattering peak characteristic of ionic clusters. The samples were then characterized for their water uptake, chemical and mechanical stability, and conductivity. They showed a combination of high water content and extreme brittleness, which also resulted in fairly low conductivity. The brittleness resulted from large water swelling as well as the need for each nickel cation to act as a crosslinker, necessary with the current nickel‐coordination chemistry. Therefore, increasing the ion exchange capacity (IEC) for these types of AEMs, important for enhancing conductivity, also increased the crosslink density. The low conductivity and brittleness seen in this work demonstrated the need to develop non‐crosslinking metal‐complexes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 328–339

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“…Monomer 1 was synthesized following an adaption of previously published procedures . A mixture of Tosyl–Cl (9.2 g, 0.048 mol, 1.2 eq.…”

Section: Methodsmentioning

confidence: 99%

Utilizing thiol–ene chemistry for crosslinked nickel cation‐based anion exchange membranes

Kwasny

Zhu

Hickner

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…The last decade has experienced an unprecedented growth of the types of aerogels available, ranging from inorganic [22][23][24][25] to organic (based on biopolymers [3,14,[26][27][28] and synthetic polymers) and hybrid inorganic-organic aerogels [29][30][31][32][33][34]. The growth of synthetic polymer aerogels in particular has been extremely rapid and now that class includes aerogels based on a wide variety of phenolic resins [35][36][37], polyamides [38][39][40], polyimides [41][42][43][44][45][46][47], polyurethanes [48][49][50][51][52][53], polyureas [54][55][56][57][58] and polymers derived via ring opening metathesis polymerization (ROMP) [42,49,[59][60][61][62][63][64]…”

Section: Introductionmentioning

confidence: 99%

“…It is considered as one of the most important synthetic tools in polymer and materials science and has been used for the industrial production of several commercial A wide variety of catalysts have been reported in the literature for the ROMP of DCPD. Most of those catalysts are based on mononuclear complexes of transition metals [59,61,[72][73][74], which can be catalytically active per se, or after activation with a co-initiator. Although less widely known, bimetallic clusters with metal-metal bonds have also been employed as ROMP catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…Such crosslinked PDCPD is a rigid polymer with excellent mechanical, chemical and physical properties. PDCPD aerogels combine the unique properties of aerogels with those of PDCPD polymers [59][60][61][62][63][64][65]. Thus, mechanically strong PDCPD-based aerogels can find applications as thermal and acoustic insulators [60], as well as low-density coatings [59,64].…”

Section: Introductionmentioning

confidence: 99%

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Large, Rapid Swelling of High-cis Polydicyclopentadiene Aerogels Suitable for Solvent-Responsive Actuators

et al. 2020

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High-cis polydicyclopentadiene (PDCPD) aerogels were synthesized using ring opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) with a relatively air-stable ditungsten catalytic system, Na[W2(μ-Cl)3Cl4(THF)2]·(THF)3 (W2; (W3W)6+, a′2e′4), and norbornadiene (NBD)as a co-initiator. These aerogels are compared in terms of chemical structure and material properties with literature PDCPD aerogels obtained using well-established Ru-based alkylidenes as catalysts. The use of NBD as a co-initiator enhances the degree of crosslinking versus the more frequently used phenylacetylene (PA), yielding materials with a controlled molecular structure that would persist solvent swelling. Indeed, those PDCPD aerogels absorb selected organic solvents (e.g., chloroform, tetrahydrofuran) and swell rapidly, in some cases up to 4 times their original volume within 10 min, thus showing their potential for applications in chemical sensors and solvent-responsive actuators. The advantage of aerogels versus xerogels or dense polymers for these applications is their open porosity, which provides rapid access of the solvent to their interior, thus decreasing the diffusion distance inside the polymer itself, which in turn accelerates the response to the solvents of interest.

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“…In that regard, although there is a vast literature for monolithic aerogels derived from synthetic polymers, including aerogels based on phenolic resins (e.g., resorcinol-formaldehyde [19,55,56,57,58,59,60,61], polybenzoxazines [62,63,64,65,66], polyureas [67,68,69], polyimides [70,71,72,73,74], polyamides (Kevlar TM -like) [74,75,76], polyurethanes [77,78,79,80,81,82,83], as well as aerogels derived via Ring Opening Metathesis Polymerization (ROMP), including polynorbornene and polydicyclopentadiene [81,84,85,86,87], only a few examples of synthetic polymer aerogel particles are known, and they have become the subject of this mini-review. Those polymeric materials include mostly polyurea aerogels, and a few examples of polyimide and phenolic resin aerogels.…”

Section: Introductionmentioning

confidence: 99%

Synthetic Polymer Aerogels in Particulate Form

et al. 2019

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Aerogels have been defined as solid colloidal or polymeric networks of nanoparticles that are expanded throughout their entire volume by a gas. They have high surface areas, low thermal conductivities, low dielectric constants, and high acoustic attenuation, all of which are very attractive properties for applications that range from thermal and acoustic insulation to dielectrics to drug delivery. However, one of the most important impediments to that potential has been that most efforts have been concentrated on monolithic aerogels, which are prone to defects and their production requires long and costly processing. An alternative approach is to consider manufacturing aerogels in particulate form. Recognizing that need, the European Commission funded “NanoHybrids”, a 3.5 years project under the Horizon 2020 framework with 12 industrial and academic partners aiming at aerogel particles from bio- and synthetic polymers. Biopolymer aerogels in particulate form have been reviewed recently. This mini-review focuses on the emerging field of particulate aerogels from synthetic polymers. That category includes mostly polyurea aerogels, but also some isolated cases of polyimide and phenolic resin aerogels. Particulate aerogels covered include powders, micro granules and spherical millimeter-size beads. For the benefit of the reader, in addition to the literature, some new results from our laboratory concerning polyurea particle aerogels are also included.

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Exploration of the versatility of ring opening metathesis polymerization: an approach for gaining access to low density polymeric aerogels

Cited by 33 publications

References 33 publications

Utilizing thiol–ene chemistry for crosslinked nickel cation‐based anion exchange membranes

Utilizing thiol–ene chemistry for crosslinked nickel cation‐based anion exchange membranes

Large, Rapid Swelling of High-cis Polydicyclopentadiene Aerogels Suitable for Solvent-Responsive Actuators

Synthetic Polymer Aerogels in Particulate Form

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