Large-Scale Preparation of Long-Chain ADMET Synthons

Sauty, Nicolas F.; Li, Hong; Silva, Lucas Caire da; Wagener, Kenneth B.

doi:10.1080/00397911.2014.899606

Cited by 6 publications

(7 citation statements)

References 23 publications

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“…Aliphatic sulfone‐containing α,ω‐diene monomers 7 , 8 , and 9 (see Scheme ) were synthesized in a similar fashion to that of other ADMET monomers by alkylation of a functionality with a terminal alkene substrate . However, compared to other ADMET monomers, the synthesis of precise sulfone monomers is far more straightforward.…”

Section: Resultsmentioning

confidence: 99%

High Melting Precision Sulfone Polyethylenes Synthesized by ADMET Chemistry

Gaines

Trigg

Winey

et al. 2016

Macromol. Chem. Phys.

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A series of aliphatic polysulfones is synthesized via ADMET polymerization in which a sulfone group is located precisely after every 8th, 14th, and 20th carbon. Primary structural characterization is accomplished using 1H NMR, 13C NMR, and IR. Polymer morphology is studied by DSC and X‐ray scattering, which reveals layered morphologies comprised of polyethylene crystallites along with sulfone groups arranged in sheets. In contrast to other precision polymers with functional groups synthesized by ADMET, this morphology is found at all spacer lengths. Prior to hydrogenation the sulfone polymers show Tm decreasing with increasing sulfone concentration, a typical phenomenon attributed to the mix of cis and trans configurations producing defects in the crystals. However, following hydrogenation, the melting temperature increases as the sulfone group concentration increased rather than decreased, with the highest Tm being 175 °C. This is an increase of 45 °C relative to linear polyethylene synthesized via ADMET chemistry. The precise location of the sulfone groups, which are not tactic, within these polyethylenes increases crystallinity, promotes secondary bonding and increases Tm.

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Section: Resultsmentioning

confidence: 99%

High Melting Precision Sulfone Polyethylenes Synthesized by ADMET Chemistry

Gaines

Trigg

Winey

et al. 2016

Macromol. Chem. Phys.

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“…In the past years, new methodologies for the preparation of ADMET monomers have been widely explored and developed by our research group, which now makes the synthesis of long-chain branched polyethylene possible. By taking advantage of our published methodologies for making lengthy spaced α,ωalkenyl alcohols 13 and nitrile alkylation/decyanation chemistry, 14,15 we are able to prepare symmetrical diene monomers with −C 21 H 43 groups placed in the middle of the monomer 6, 8, 9, 10, and 18 methylene spacers from the terminal double bonds (Scheme 1). Solubility issues are inevitable in the syntheses.…”

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“…The evolution from monomer to final polymer was monitored by 1 H and 13 C NMR. As an example, Figure 1 shows the 1 H and 13 C NMR spectra of polymer 7a and its precursors.…”

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confidence: 99%

“…The evolution from monomer to final polymer was monitored by 1 H and 13 C NMR. As an example, Figure 1 shows the 1 H and 13 C NMR spectra of polymer 7a and its precursors. The successful ADMET polymerization with Grubbs' first generation catalyst is evidenced by the disappearance of the terminal olefin proton signals at 4.9 and 5.8 ppm (Figure 1a) and the appearance of the internal proton signals at 5.4 ppm (Figure 1c) in 1 H NMR.…”

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confidence: 99%

“…The successful ADMET polymerization with Grubbs' first generation catalyst is evidenced by the disappearance of the terminal olefin proton signals at 4.9 and 5.8 ppm (Figure 1a) and the appearance of the internal proton signals at 5.4 ppm (Figure 1c) in 1 H NMR. 13 C NMR (Figure 1b and 1d) shows that, after polymerization, signals attributed to terminal olefin at 114.29 and 139.49 ppm disappeared with the formation of new internal olefin signals at around 130 ppm (cis at 130.10 ppm and trans at 130.56 ppm). Subsequent exhaustive hydrogenation under high H 2 pressure using Pd/C as a catalyst generated ADMET polyethylene with 21-carbon branches on every 15th carbon along the polymer backbone (7a).…”

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Precision Long-Chain Branched Polyethylene via Acyclic Diene Metathesis Polymerization

Rojas

Wagener

2015

ACS Macro Lett.

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A series of polyethylenes containing 21-carbon alkyl branches have been synthesized by acyclic diene metathesis (ADMET) polymerization. These 21-carbon alkyl branches are precisely placed on every 15th, 19th, 21st, 23rd, and 39th carbon along the polymer backbone. Precision of primary structures of all polymers is verified by 1H and 13C NMR spectroscopy. All polymers present well-defined melting profiles, even at a high branch incorporation (13.3% mol). The melting temperature increases as the branch frequency decreases, similar to what we observed for short-chain branched polyethylenes. These observations together with a good linear relationship derived from Flory's theory suggest the exclusion of 21-carbon side chains from polyethylene crystal units

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ADMET Polymerization

Rojas

Wagener

Pribyl

2022

Encyclopedia of Polymer Science and Technology

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Acyclic diene metathesis (ADMET) polymerization is a synthetic strategy used to prepare polyolefins decorated with precisely spaced functional groups. Offered here is a survey of monomer design and synthesis, expert advice on α,ω‐diene monomer synthesis and purification, and a guide to selecting the optimal catalyst. In light of the advances in olefin metathesis catalysts and the library of ADMET polymers prepared, a discussion of what has been learned from these carefully prepared precision polymers is presented.

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Large-Scale Preparation of Long-Chain ADMET Synthons

Cited by 6 publications

References 23 publications

High Melting Precision Sulfone Polyethylenes Synthesized by ADMET Chemistry

High Melting Precision Sulfone Polyethylenes Synthesized by ADMET Chemistry

Precision Long-Chain Branched Polyethylene via Acyclic Diene Metathesis Polymerization

ADMET Polymerization

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