Synthesis of Functionalizable and Degradable Polymers by Ring‐Opening Metathesis Polymerization

Fishman, Joshua M.; Kiessling, Laura L.

doi:10.1002/ange.201300293

Cited by 17 publications

(10 citation statements)

References 49 publications

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“…To this end, we reported that bicyclic oxazinones undergo ROMP to afford polyoxazinones, 39 which are stable yet degradable under acidic or basic conditions. We diversified the polyoxazinone backbone by generating a monomer library with various hydroxamic ester substituents (Figure 1A).…”

Section: ■ Introductionmentioning

confidence: 99%

Chemoselective, Postpolymerization Modification of Bioactive, Degradable Polymers

Fishman¹,

Zwick²,

Kruger³

et al. 2019

Biomacromolecules

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Degradable polymers promote sustainability, mitigate environmental impact, and facilitate biological applications. Tailoring degradable polymers is challenging because installing functional group-rich side chains is difficult when the backbone itself is susceptible to degradation. A convenient means of side chain installation is through post-polymerization modification (PPM). In functionalizing polyoxazinones, a class of degradable polymers generated by the ring-opening metathesis polymerization (ROMP), we predictably found PPM challenging. Even the versatile azide-alkyne cycloaddition click reaction was ineffective. To solve this problem, we screened PPM reactions whose efficiencies could be assessed using photochemistry (excimer formation). The mildest, pH-neutral process was functionalization of a ketone-containing polymer to yield either oxime (acid labile)-or alkyoxylamine (stable)-substituted polymers. Using this approach, we equipped polymers with fluorophores, reporter groups, and bioactive epitopes. These modifications imbued the polymers with distinctive spectral properties and biological activities. Thus, polyoxazinones are now tunable through a modular method to diversify a macromolecule's function

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Section: ■ Introductionmentioning

confidence: 99%

Chemoselective, Postpolymerization Modification of Bioactive, Degradable Polymers

Fishman¹,

Zwick²,

Kruger³

et al. 2019

Biomacromolecules

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“…A key aspect of these SBPs is that the hemiaminal ether in the monomers is incorporated into the polymer backbone. Hemiaminal ethers, 52 and related derivatives, 34,36 are known to be acid sensitive; thus, we conducted several experiments to test the degradability of these polymers. We sequentially added small amounts of HCl to P2 in THF, and monitored the degradation by SEC (Figure 3A; see the SI for details).…”

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confidence: 99%

Controlled Living Cascade Polymerization To Make Fully Degradable Sugar-Based Polymers from d-Glucose and d-Galactose

et al. 2019

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Monomers derived from glucose and galactose, which contain an endocyclic alkene (in the sugar ring) and a terminal alkyne, underwent a cascade polymerization to prepare new polymers with the ringopened sugar incorporated into the polymer backbone. Polymerizations were well-controlled, as demonstrated by a linear increase in molecular weight with monomer-toinitiator ratio and generally narrow molecular weight dispersity values. The living nature of the polymerization was supported by the preparation of a block copolymer from two different sugar-based monomers. The resulting polymers were also fully degradable. They underwent fast and complete depolymerization to small molecules under acidic conditions.

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“…Yield: 25.2 g, 99%. 1 TEGylated Ruthenium-Based Catalyst (5). Grubbs' secondgeneration catalyst (G2) (9) (40 mg, 0.05 mmol) was weighed into a 20 mL vial in a nitrogen-filled glovebox.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Ruthenium-based metathesis catalysts are employed extensively in ring-opening metathesis polymerization (ROMP) due to their remarkable tolerance to air, moisture, and various functional groups. 1 These features have propelled ROMPbased polymers into many fields such as biomaterials, 2 liquid crystalline polymers, 3 self-healing materials, 4 degradable plastics, 5 and nanocomposites. 6 Unlike many other commercial polymerization processes that have been adapted to waterbased systems for both environmental and economic reasons, comparatively little attention has been given to extend ROMP into aqueous dispersed systems.…”

Section: ■ Introductionmentioning

confidence: 99%

Ring-Opening Metathesis Polymerization in Miniemulsion Using a TEGylated Ruthenium-Based Metathesis Catalyst

Zhu

Zenkina

et al. 2018

Macromolecules

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Ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene (COD) in miniemulsion was conducted utilizing a water-soluble TEGylated ruthenium alkylidene catalyst that was designed to undergo phase transfer from the aqueous phase to the monomer droplets or polymer particles following activation. The catalyst yielded colloidally stable latexes with ∼100% conversion, often in less than 1 h. Kinetic studies revealed first-order kinetics with good livingness as confirmed by the shift of gel permeation chromatography (GPC) traces. Depending on the surfactants used, the particle sizes ranged from 100 to 300 nm with monomodal distributions. The more strained cyclic olefin norbornene (NB) could also be efficiently polymerized in miniemulsion with full conversion and without coagulum formation.

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Synthesis of Functionalizable and Degradable Polymers by Ring‐Opening Metathesis Polymerization

Cited by 17 publications

References 49 publications

Chemoselective, Postpolymerization Modification of Bioactive, Degradable Polymers

Chemoselective, Postpolymerization Modification of Bioactive, Degradable Polymers

Controlled Living Cascade Polymerization To Make Fully Degradable Sugar-Based Polymers from d-Glucose and d-Galactose

Ring-Opening Metathesis Polymerization in Miniemulsion Using a TEGylated Ruthenium-Based Metathesis Catalyst

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