Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

Debsharma, Tapas; Yaǧcı, Yusuf; Schlaad, Helmut

doi:10.1002/anie.201908458

Cited by 25 publications

(19 citation statements)

References 38 publications

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“…Photoinduced polymerization methodology has been replacing the conventional approaches especially after its distinguished advantages have been realized [22–27] . Such distinct advantages include spatial and temporal control of the processes, low energy requirement and site‐specific activation, in contrast to thermal based synthesis [28–31] .…”

Section: Introductionmentioning

confidence: 99%

Directly and Indirectly Acting Photoinitiating Systems for Ring‐Opening Polymerization of ϵ‐Caprolactone

2021

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Directly and indirectly acting photoinitiating systems for cationic ring opening polymerization (ROP) of ϵ‐caprolactone (ϵ‐CL) by using diphenyl iodonium salt (DPI) in the presence of benzyl alcohol were studied and mechanistic details were evaluated. In the direct system, the polymerization is initiated by a Brønsted acid formed upon UV irradiation of DPI. Polymerizations by indirectly acting photoinitiating systems proceeding via electron transfer reactions of photochemically formed electron donor radicals or excited states of polynuclear aromatic compounds with DPI were investigated. It was demonstrated that polymerizations proceed in a controlled manner by an activated monomer (AM) mechanism. Applicability of the photoinitiation to the other lactone monomers was validated on the example of δ‐ valerolactone (δ‐VL).

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Section: Introductionmentioning

confidence: 99%

Directly and Indirectly Acting Photoinitiating Systems for Ring‐Opening Polymerization of ϵ‐Caprolactone

2021

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“…Levoglucosenol 2a was synthesized by the reduction of levoglucosenone 1 with sodium borohydride . The levoglucosenyl alkyl ethers 2b–f were synthesized by the alkylation of 2a with the respective alkyl iodides, see the Supporting Information.…”

Section: Methodsmentioning

confidence: 99%

“…Levoglucosenol 2a was synthesized by the reduction of levoglucosenone 1 with sodium borohydride. 6 The levoglucosenyl alkyl ethers 2b−f were synthesized by the alkylation of 2a with the respective alkyl iodides, 14 Size exclusion chromatography (SEC) with simultaneous UV and RI detection was performed with THF as the eluent (a flow rate of 0.5 mL•min −1 ) at room temperature. The stationary phase was a 300 × 8 mm 2 PSS SDV linear M column (3 μm particle size, molar mass range 10 2 −10 6 Da).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Ring-Opening Metathesis Polymerization of Unsaturated Carbohydrate Derivatives: Levoglucosenyl Alkyl Ethers

et al. 2021

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A series of biomass-derived levoglucosenyl alkyl ethers (alkyl = methyl, ethyl, n-propyl, isopropyl, and n-butyl) were synthesized and polymerized by ring-opening olefin metathesis polymerization using the Grubbs catalyst C793 at room temperature. Polymerizations were successfully performed in conventional solvents such as 1,4-dioxane and dichloromethane as well as in polar aprotic “green” solvents such as 2-methyltetrahydrofuran, dihydrolevoglucosenone (Cyrene), and ethyl acetate. The prepared polyacetals with degrees of polymerization of ∼100 exhibit Schulz–Flory-type molar mass distributions and are thermoplastic materials with rather low glass transition temperatures in the range of 43–0 °C depending on the length of the alkyl substituent. Kinetic studies revealed that the polymerization proceeded rapidly to a steady state with a certain minimum monomer concentration threshold. When the steady state was reached, just about half of the [Ru] catalyst had been effective to initiate the polymerization, indicating that the initiation step was a slow process. The remaining catalyst was still active and did no longer react with monomers but with in-chain double bonds, cutting the formed polymer chains into shorter fragments. In the long term, all catalyst was consumed and propagating [Ru] chain ends were deactivated by the elimination of [Ru] from the chain ends to form inactive chains with terminal aldehyde groups.

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“…LGO is an α , β ‐unsaturated cyclic ketone, isolated during the acid‐catalyzed pyrolysis of cellulose. [ 97 ] While LGO can be directly polymerized by ring opening metathesis polymerization [ 98 ] and cationic ring opening polymerization, [ 99 ] the structure of LGO does not lend itself to be directly polymerized by radical polymerization techniques. However, the LGO synthon can be revalorized into various (meth)acrylic monomers compatible with RDRP methods ( Figure ).…”

Section: Well‐defined Poly(meth)acrylates Based On Lignocellulosic Su...mentioning

confidence: 99%

RDRP (Meth)acrylic Homo and Block Polymers from Lignocellulosic Sugar Derivatives

Palà

Woods

Hatton

et al. 2022

Macro Chemistry & Physics

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Currently, most commodity chemicals and polymers are manufactured from nonrenewable petroleum-based resources. However, due to its finite nature and social claims about environment preservation, alternative sources of value-added and building block chemicals are being intensively studied. Renewable lignocellulosic biomass has offered an attractive replacement for fossil-based chemicals. Lignin and C5/C6 sugars obtained from lignocellulosic biomass through chemical and enzymatic methods can be further transformed to targeted chemical platforms. In the present review, synthetic pathways for well-defined poly(meth)acrylates obtained from C5/C6 sugar-derived platforms in which the sugar structure is not retained are discussed. While bio-based polymers from these monomers are investigated using a wide range of polymerization techniques, this study focuses on precise synthesis of macromolecular structures taking advantage of reversible-deactivation radical polymerization methods and their applications.

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Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

Cited by 25 publications

References 38 publications

Directly and Indirectly Acting Photoinitiating Systems for Ring‐Opening Polymerization of ϵ‐Caprolactone

Directly and Indirectly Acting Photoinitiating Systems for Ring‐Opening Polymerization of ϵ‐Caprolactone

Ring-Opening Metathesis Polymerization of Unsaturated Carbohydrate Derivatives: Levoglucosenyl Alkyl Ethers

RDRP (Meth)acrylic Homo and Block Polymers from Lignocellulosic Sugar Derivatives

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