Dual-component systems for storable frontal ring-opening metathesis polymerization resins

Frontal ring-opening metathesis polymerization (FROMP) with Grubbs-type Ru catalysts allows for the rapid and energetically efficient production of structural polymers. Applications for these polymers often require long periods of time during which the resins are stored or transported prior to polymerization. As such, the ideal catalytic system for the FROMP of these resins remains inactive for extended periods of time until the purposeful initiation of polymerization. However, the high reactivity exhibited by most conventional FROMP catalysts often leads to premature polymerization at ambient temperatures within mere hours or days. In this work, we examined a thermally latent bis-N-heterocyclic carbene Ru complex which had high reactivity upon thermal initiation but only after activation by a Cu(I) co-reagent. Without the presence of Cu, the resins remained in liquid-state for up to 8 weeks. We examined over 40 dual-component formulations for the FROMP of dicyclopentadiene. Polymerization parameters, resin stability, and polymer properties were investigated for each formulation and statistical analysis was performed to provide insight into trends and correlations within the system. Interestingly, we found that with excess Cu relative to Ru, the reaction fronts were colder and slower. Mechanistic studies showed that excess Cu inhibited the system during both catalyst activation and polymerization.

Name thesis:degree_name

M.S.

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2022

Author dc:creator

• Yazdani, Aliza N.

Contributors dc:contributor

• Moore, Jeffrey S.

• Polymerization
• FROMP
• thermosets
• polymers

Statement dc:rights

• Copyright 2022 Aliza N. Yazdani

Language dc:language

en, eng

Handle dc:identifier

https://hdl.handle.net/2142/117696

OAI record oai:identifier

https://www.ideals.illinois.edu/oai-pmh?verb=GetRecord&metadataPrefix=etdms&identifier=oai%3Awww.ideals.illinois.edu%3A2142%2F117696