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. 2019 Oct 28;58(44):15726-15730.
doi: 10.1002/anie.201909172. Epub 2019 Sep 19.

Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

Liangbing Fu  1 , Xuelin Sui  1 , Alex E Crolais  1 , Will R Gutekunst  1
Affiliations

Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

Liangbing Fu et al. Angew Chem Int Ed Engl. .

Abstract

A modular synthetic approach to degradable metathesis polymers is presented using acetal-containing enyne monomers. The monomers are prepared in a short and divergent synthetic sequence that features two points of modification to tune polymerization behavior and introduce molecular cargo. Steric and stereochemical elements are critical in the monomer design in order to provide rapid and living polymerizations capable of generating block polymers. The developed polyacetal materials readily undergo pH-dependent degradation in aqueous mixtures, and the rate of hydrolysis can be tuned through post-polymerization modification with triazolinedione click chemistry. This presents a new scaffold for responsive metathesis polymers that may find use in applications that requires controllable breakdown and release of small molecules.

Keywords: acetal; degradable polymer; enyne monomers; living polymerization; metathesis polymerization.

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Figures

Figure 1.
Figure 1.
(A-C) Previous monomer designs for metathesis polymerization. (D) New monomers for synthesis of degradable polyacetals via enyne metathesis.
Figure 2.
Figure 2.
(A) SEC chromatogram of P1Mes at different targeted degrees of polymerization (DP) and (B) linear correlation of Mn with DP.
Figure 3.
Figure 3.
(A) Synthesis of diblock P1Mes-b-P5Mes through sequential monomer addition and (B) SEC chromatogram of the first block and chain-extension.
Figure 4.
Figure 4.
Degradation of P1Mes in neutral, basic, and acidic aqueous media.
Figure 5.
Figure 5.
(A) Triazolinedione click functionalization of P1Mes with PTAD and (B) increased hydrolytic stability of P1Mes-PTAD under acidic conditions.
Scheme 1.
Scheme 1.
Modular synthesis of enyne acetal monomers.
See this image and copyright information in PMC

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