Inverse Vulcanization of Activated Norbornenyl Esters-A Versatile Platform for Functional Sulfur Polymers
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chair:
Grimm, AP; Plank, M; Stihl, A; Schmitt, CW; Voll, D ; Schacher, FH; Lahann, J; Théato, P
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place:
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 2024, Volume 63, Issue 36, DOI: 10.1002/anie.202411010
- Date: August 2024
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Elemental sulfur has shown to be a promising alternative feedstock for development of novel polymeric materials with high sulfur content. However, the utilization of inverse vulcanized polymers is restricted by the limitation of functional comonomers suitable for an inverse vulcanization. Control over properties and structure of inverse vulcanized polymers still poses a challenge to current research due to the dynamic nature of sulfur-sulfur bonds and high temperature of inverse vulcanization reactions. In here, we report for the first time the inverse vulcanization of norbornenyl pentafluorophenyl ester (NB-PFPE), allowing for post-modification of inverse vulcanized polymers via amidation of reactive PFP esters to yield high sulfur content polymers under mild conditions. Amidation of the precursor material with three functional primary amines (alpha-amino-omega-methoxy polyethylene glycol, aminopropyl trimethoxy silane, allylamine) was investigated. The resulting materials were applicable as sulfur containing poly(ethylene glycol) nanoparticles in aqueous environment. Cross-linked mercury adsorbents, sulfur surface coatings, and high-sulfur content networks with predictable thermal properties were achievable using aminopropyl trimethoxy silane and allylamine for post-polymerization modification, respectively. With the broad range of different amines available and applicable for post-polymerization modification, the versatility of poly(sulfur-random-NB-PFPE) as a platform precursor polymer for novel specialized sulfur containing materials was showcased.
The inverse vulcanization of norbornenyl pentafluorophenyl ester is reported, which yielded an active ester-containing platform material that could undergo post-polymerization modification with primary amines under mild conditions. Modification with alpha-amino-omega-methoxy polyethylene glycol, aminopropyl trimethoxy silane, and allylamine allowed preparation of nanoparticles, coated surfaces, and cross-linked networks, respectively.