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Polymers depolymerizable by metathesis of a cleavable unit

Patent ·
OSTI ID:2541680

Novel polymers are depolymerizable by metathesis of a cleavable unit. As an example, a series of linear and crosslinked polyurethanes were prepared that can be selectively depolymerized under mild conditions. Two unique polyols were synthesized bearing unsaturated units in a configuration designed to favor ring-closing metathesis to five- and six-membered cycloalkenes. These polyols were co-polymerized with toluene diisocyanate to generate linear polyurethanes and trifunctional hexamethylene- and diphenylmethane-based isocyanates to generate crosslinked polyurethanes. The polyol design is such that the ring-closing metathesis reaction cleaves the backbone of the polymer chain. Upon exposure to dilute solutions of Grubbs' catalyst under ambient conditions, the polyurethanes were rapidly depolymerized to low molecular weight, soluble products bearing vinyl and cycloalkene functionalities. These functionalities enabled further re-polymerization by traditional strategies for polymerization of double bonds. This general approach can be expanded to develop a range of chemically recyclable condensation polymers that are readily depolymerized by orthogonal metathesis chemistry.

Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
DOE Contract Number:
NA0003525
Assignee:
National Technology & Engineering Solutions of Sandia, LLC (Albuquerque, NM)
Patent Number(s):
11,873,367
Application Number:
17/244,012
OSTI ID:
2541680
Country of Publication:
United States
Language:
English

References (10)

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Enol Formation and Ring-Opening in OH-Initiated Oxidation of Cycloalkenes journal November 2008
Functionalized Polyethylene via Acyclic Diene Metathesis Polymerization:  Effect of Precise Placement of Functional Groups journal November 2000
Highly active ruthenium metathesis catalysts enabling ring-opening metathesis polymerization of cyclopentadiene at low temperatures journal August 2019
Depolymerization of 1,4-polybutadiene by metathesis: high yield of large macrocyclic oligo(butadiene)s by ligand selectivity control journal January 2016

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