Ring-Opening Polymerization of Cyclic Acetals

Kubisa, Przemysław; Vairon, Jean‐Pierre

doi:10.1016/b978-0-444-53349-4.00103-5

Cited by 18 publications

(37 citation statements)

References 114 publications

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“…Cyclic acetals were also generated in previous reports on the cationic polyaddition of OH-VEs in THF, 20,21 although the cyclic acetals were suggested to be unreactive. 25 The propagation reaction of MDOP is considered to proceed mainly via the active chain end (ACE) mechanism at the oxonium chain ends, 26 while the propagation of CL probably proceeds only at the hydroxy ends via the AM mechanism (Scheme 2B, left). In addition, intra-and intermolecular chain-end-coupling potentially occurs between the oxonium and hydroxy ends (Scheme 2B, right).…”

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confidence: 99%

Tandem Unzipping and Scrambling Reactions for the Synthesis of Alternating Copolymers by the Cationic Ring-Opening Copolymerization of a Cyclic Acetal and a Cyclic Ester

2019

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Cationic copolymerization of different types of monomers, 4-hydroxybutyl vinyl ether (HBVE) and ε-caprolactone (CL), was explored using EtSO3H as an acid catalyst, producing copolymers with a remarkably wide variety of compositions and sequences. In the initial stage of the reaction, HBVE was unexpectedly isomerized to 2-methyl-1,3-dioxepane (MDOP), followed by concurrent copolymerization of MDOP and CL via active chain end and activated monomer mechanisms, respectively. The compositions and sequences of the copolymers were tunable, depending on the initial monomer concentrations. Moreover, a unique method was developed for transforming a copolymer with no CL homosequences into an “alternating” copolymer by removing MDOP from the system using a vacuum pump. This was achieved by the tandem reactions of depolymerization (unzipping) and random transacetalization (scrambling) under thermodynamic control. Specifically, the unzipping of HBVE homosequences proceeded at the oxonium chain end until a nondissociable ester bond emerged next to the chain end, while the scrambling of the main chain via transacetalization transferred midchain HBVE homosequences into the polymer chain end.

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Tandem Unzipping and Scrambling Reactions for the Synthesis of Alternating Copolymers by the Cationic Ring-Opening Copolymerization of a Cyclic Acetal and a Cyclic Ester

2019

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“…These moderate molecular weights are most likely caused by intermolecular chain transfer and back-biting reactions which are common features in cROP of cyclic acetals. 57 Chain transfer reactions are favored in the cROP of cyclic acetals due to the higher basicity of oxygen atoms in the polymer chain as compared to the monomer. 57 Moreover, it is hypothesized that metal triflate mediated cROP of levoglucosan derivatives follows a catalytic approach as reported in the literature.…”

Section: Resultsmentioning

confidence: 99%

“… 57 Chain transfer reactions are favored in the cROP of cyclic acetals due to the higher basicity of oxygen atoms in the polymer chain as compared to the monomer. 57 Moreover, it is hypothesized that metal triflate mediated cROP of levoglucosan derivatives follows a catalytic approach as reported in the literature. 54 In a catalytic approach, one metal triflate molecule catalytically produces a large number of polymer molecules, thereby leading to shorter polymer chains.…”

Section: Resultsmentioning

confidence: 99%

Stereoregular functionalized polysaccharidesviacationic ring-opening polymerization of biomass-derived levoglucosan

et al. 2022

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“…In contrast to the suggestions of Plesch, Jaacks [43] and later Penczek [44] postulated, based on extensive experimental results that propagation takes place essentially via open chains. Finally, from even more detailed studies it was found that ring-expansion is favored at low monomer concentrations and the open chain mechanism dominates the propagation at higher monomer concentration [45] (see also [5]). This discussion is worthy of detailed study since it demonstrates the need to carefully examine the experimental techniques and the prevailing conditions before making conclusions about reaction mechanisms, especially where cationic systems are involved.…”

Section: Cationic Ring-opening Polymerizationmentioning

confidence: 99%

“…It is hoped that it will provide a useful start for entering the field rather than being an exhaustive review of all the literature to date. It is recommended that the interested reader refer to, e.g., the chapters of [5]. …”

Section: Introductionmentioning

confidence: 99%

Ring-Opening Polymerization—An Introductory Review

Nuyken

Pask²

2013

Polymers

365

265

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We would like to dedicate this article to P. H. Plesch, a pioneer of cationic polymerization and a mentor and friend for many of those who are now at the forefront of this field of science. He passed away 5 March 2013 at the age of 95. We will miss him. Abstract: This short, introductory review covers the still rapidly growing and industrially important field of ring opening polymerization (ROP). The review is organized according to mechanism (radical ROP (RROP), cationic ROP (CROP), anionic ROP (AROP) and ring-opening metathesis polymerization (ROMP)) rather than monomer classes. Nevertheless, the different groups of cyclic monomers are considered (olefins, ethers, thioethers, amines, lactones, thiolactones, lactams, disulfides, anhydrides, carbonates, silicones, phosphazenes and phosphonites) and the mechanisms by which they can be polymerized involving a ring-opening polymerization. Literature up to 2012 has been considered but the citations selected refer to detailed reviews and key papers, describing not only the latest developments but also the evolution of the current state of the art.

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Ring-Opening Polymerization of Cyclic Acetals

Cited by 18 publications

References 114 publications

Tandem Unzipping and Scrambling Reactions for the Synthesis of Alternating Copolymers by the Cationic Ring-Opening Copolymerization of a Cyclic Acetal and a Cyclic Ester

Tandem Unzipping and Scrambling Reactions for the Synthesis of Alternating Copolymers by the Cationic Ring-Opening Copolymerization of a Cyclic Acetal and a Cyclic Ester

Stereoregular functionalized polysaccharidesviacationic ring-opening polymerization of biomass-derived levoglucosan

Ring-Opening Polymerization—An Introductory Review

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