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1.
Chem Sci ; 15(23): 8766-8774, 2024 Jun 12.
Article in English | MEDLINE | ID: mdl-38873082

ABSTRACT

Full dechlorination of poly(vinyl chloride) (PVC) in a controlled manner to yield useful polymeric and chlorinated products is of great interest for the processing of PVC waste. Forming polyethylene (PE) without corrosive by-products would allow for a pre-treatment of PE wastes that are often contaminated with PVC. Herein, full dechlorination of PVC has been achieved via generation of silylium ions in situ, to furnish PE products. Complete dechlorination of PVC can be achieved in 2 hours, yielding organic polymer that has similar spectroscopic and thermal signatures of branched PE, with no observable chlorine. The degree of branching can be tuned between 31 and 57 branches per 1000 carbons, with melting temperatures ranging from 51 to 93 °C. This method is applicable to not only pure PVC, but also commercial PVC products. Depending on if the PVC products are separated from plasticizers, different melting points of the resulting PE are observed. PVC dechlorination in the presence of PE waste is also shown. This is the first report of being able to cleanly convert PVC waste to PE in high yields and tune the thermal properties of the PE product, highlighting the remarkable control that silylium ion mediated transformations enables compared to past chemical methods.

2.
ACS Sustain Chem Eng ; 12(19): 7246-7255, 2024 May 13.
Article in English | MEDLINE | ID: mdl-38757124

ABSTRACT

Aliphatic polyesters have received considerable attention in recent years due to their biodegradability and biocompatible, mechanical, and thermal properties that can make them a suitable alternative to today's commercialized polymers. The ring-opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is a route to synthesize a diverse array of polyesters that could be useful in many applications. However, the catalysts used rarely consider biocompatible catalysts in the case that any are left in the polymer. To the best of our knowledge, we report the first example of using deep eutectic solvents (DESs) as biocompatible catalysts for this target ROCOP with polymerization activity for at least six diverse monomer pairs. Choline halide salts are active for this polymerization, with dried salts showing polymerization slower than that of those conducted in air. Hydrogen bonding with water is hypothesized to enhance the rate-determining step of epoxide ring opening. While the presence of water improves the rate of polymerization, it also acts as a chain transfer agent, leading to smaller molar mass polymers than intended. Combining the choline halide salts with urea or ethylene glycol hydrogen bond donors in air led to DES catalysts that reacted similarly to the salts exposed to air. However, when generating these DESs in air-free conditions, they showed similar rates of polymerization without a drop in polymer molar mass. The hydrogen bonding provided by urea and ethylene glycol seems to promote the rate increase without serving as a chain transfer agent. Results reported herein display the promising potential of biocompatible catalyst systems for this ROCOP process as well as introducing the use of hydrogen bonding to enhance polymerization rates.

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