Scalable Frontal Oligomerization: Insights from Advanced Mass Analysis

Suslick, Benjamin A.; Alzate-Sánchez, Diego M.; Moore, Jeffrey S.

doi:10.1021/acs.macromol.2c01654

Cited by 9 publications

(33 citation statements)

References 51 publications

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“…Indeed, our earlier work highlighted the benefits of this method to study thermoset fabrication via frontal ring-opening metathesis polymerization. While analytical limitations associated with cross-linked thermosets complicate detailed understanding of the chemistry involved in curing, Kendrick analysis of oligomeric models provided a clear path to overcome this challenge . It is our hope that our recent example and this editorial will spark permeation of Kendrick analysis into the broader synthetic organic and polymer fields.…”

Section: Why Mass Analysis Is Not Yet Ubiquitousmentioning

confidence: 99%

“…We have previously discussed these limitations in greater detail in the Supporting Information of our recent Macromolecules article. 9 ■ FUTURE DIRECTIONS IN POLYMER SYNTHESIS: COPOLYMERS While the conventional wisdom in polymer chemistry advises against analysis of copolymer MALDI spectra, Kendrick analysis provides a straightforward workflow to dissect copolymers. Fouquet and colleagues 5,8 adapted Kendrick analysis to short-chain (M̅ n < 1.5 kDa) copolymers of the type p(ethylene-r-vinyl acetate).…”

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There is Signal in Your Noise: A Case for Advanced Mass Analysis

2022

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Section: Why Mass Analysis Is Not Yet Ubiquitousmentioning

confidence: 99%

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confidence: 99%

There is Signal in Your Noise: A Case for Advanced Mass Analysis

2022

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“…The synthesis of these oligomeric buildingblocks is scalable; in some cases, > 100 g of oligomer are produced in under a few minutes after thermal initiation. 167…”

Section: Frontal Ring-opening Metathesis Oligomerizationmentioning

confidence: 99%

“…For p(DCPD) as an example, it is estimated that ≈ 15% of the pendent cyclopentene fragments undergo ringopening. 171 Suslick, Alzate-Sanchez, and Moore 167 recently developed methodology to frontally synthesize and characterize soluble oligomers of DCPD. Specifically, the incorporation of a terminal olefin chain-transfer agent (CTA) into FROMP resins prevents cross-linking and network formation.…”

Section: Frontal Ring-opening Metathesis Oligomerizationmentioning

confidence: 99%

“…The results from this work provided convincing evidence that cross-linking in FROMP occurs via cyclopentene ring-opening and not by a direct-addition mechanism. 167 The resultant telechelic oligomers possess two benefits over the parent monomer. First, o(DCPD) is odorless, unlike the foul acrid smell of DCPD.…”

Section: Frontal Ring-opening Metathesis Oligomerizationmentioning

confidence: 99%

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Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Suslick

Hemmer

Groce

et al. 2022

Preprint

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The synthesis and processing of thermoplastics and thermoset polymeric materials rely on energy-inefficient and environmentally burdensome manufacturing methods. Frontal polymerization has emerged as an attractive, scalable alternative due to its exploitation of the heat of polymerization, which generally is wasted as unutilized heat-loss. The only external energy needed for frontal polymerization is an initial thermal (or photo) stimulus that locally ignites the reaction. The subsequent reaction exothermicity provides local heating; the transport of this thermal energy to neighboring monomers in either a liquid or gel-like state results in a self-perpetuating reaction zone that provides fully-cured polymeric thermosets and thermoplastics. Propagation of this polymerization front continues through the unreacted monomer media until either all reactants are consumed or sufficient heat-loss stalls further reaction. Several different polymerization mechanisms support frontal processes, including free-radical, cat- or anionic, amine-cure epoxides, and ring-opening metathesis polymerization. The choice of monomer, initiator/catalyst, and additives dictates how fast the polymer front traverses the reactant medium, as well as the maximum temperature achievable. Frontal polymerization enables the preparation of moldable thermoplastics derived from linear polymers. When crosslinking is involved, polymeric networks (e.g., rigid thermosets) are obtainable through a related process best described as a frontal curing reaction. Numerous applications of frontally-generated polymers and thermosets exist, ranging from the reinforcement of porous substrates to the design of patterned composite materials. In this review, we examine in detail the physical and chemical phenomena that govern frontal polymerization, as well as outline the existing applications.

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A Versatile Reversible, Degenerative Chain Transfer Mechanism for the Catalytic Living Ring‐Opening Metathesis Polymerization

Mandal,

Kilbinger

2024

Angewandte Chemie

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Most metathesis polymers based on norbornene derivatives carry a vinyl end group. Here we show that these vinyl end groups readily undergo a degenerative exchange of the terminal methylene unit in the presence of sub‐stoichiometric amounts of a propagating metathesis polymer carrying a Grubbs ruthenium complex. We show that this degenerative exchange can be exploited in synthesizing ROMP polymers in a catalytic living fashion. Chain transfer agents based on styrene, or monosubstituted conjugated 1,3 diene derivatives are used as initiating sites for the catalytic living polymerization. Suitable derivatives of these chain transfer agents not only allow the linear living growth of polymers but also the synthesis of block copolymers from macro‐initiators or star polymers from multi‐functional chain transfer agents. This reversible exchange mechanism offers a cheaper, greener, and more sustainable alternative for the synthesis of living ROMP polymers compared to the classical synthetic route.

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Scalable Frontal Oligomerization: Insights from Advanced Mass Analysis

Abstract: Experimental details and oligomer characterization data (PDF)Interactive Kendrick analyses (and instructions) (XLSX) Video S1: a representative FROMO video (MP4)

Cited by 9 publications

References 51 publications

There is Signal in Your Noise: A Case for Advanced Mass Analysis

There is Signal in Your Noise: A Case for Advanced Mass Analysis

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

A Versatile Reversible, Degenerative Chain Transfer Mechanism for the Catalytic Living Ring‐Opening Metathesis Polymerization

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