Efficient One-Pot Synthesis of End-Functionalized <i>trans</i>-Stereoregular Polydiene Macromonomers

Georges, Sébastien; Hashmi, Obaid-Hasan; Bria, Marc; Zinck, Philippe; Champouret, Yohan; Visseaux, Marc

doi:10.1021/acs.macromol.8b01520

Cited by 32 publications

(20 citation statements)

References 50 publications

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“…The living trans-1,4 stereoregular polymer chain was reacted with benzophenone to afford up to 97% CPh 2 OH end-group with isoprene, while in the case of myrcene, using the same strategy, afforded trans-1,4-polymyrcene with a functionalization rate of 83%. 277 Zhang et al achieved polybutadienes having high trans-1,4 content (ca. 96%) and copolymers of butadiene with cyclic esters by a neodymium-based catalyst system (Nd(O i Pr) 3 / Mg( n Bu) 2 ).…”

Section: Stereoblock Diene Polymersmentioning

confidence: 99%

“…Visseaux et al described the preparation of end-functionalized trans -1,4-polydienes (isoprene and myrcene) by means of a neodymium catalyst (Nd(BH 4 ) 3 /MgR 2 ). The living trans -1,4 stereoregular polymer chain was reacted with benzophenone to afford up to 97% CPh 2 OH end-group with isoprene, while in the case of myrcene, using the same strategy, afforded trans -1,4-polymyrcene with a functionalization rate of 83% …”

Section: Homo- and Copolymerization Of Functionalized Monomersmentioning

confidence: 99%

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Dienes Polymerization: Where We Are and What Lies Ahead

Ricci¹,

Pampaloni

Sommazzi

et al. 2021

Macromolecules

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Recently, the research activity in the field of the stereospecific polymerization of conjugated dienes has focused on the use of catalysts based on organometallic complexes having a well-defined structure and containing ligands of various types (e.g., phosphines, bis-imines, and pyridylimines), since it has been observed that the nature of the ligand, as expected on the basis of the diene polymerization mechanism proposed several years ago by Porri, is able to exert a strong influence on the polymerization regioand stereoselectivity, on the polymer molecular weights and their distribution, and in some cases to impart a living feature to the catalysts themselves. In this Perspective we highlight the most recent results obtained in this field and discuss possible future developments in this area.

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Section: Stereoblock Diene Polymersmentioning

confidence: 99%

Section: Homo- and Copolymerization Of Functionalized Monomersmentioning

confidence: 99%

Dienes Polymerization: Where We Are and What Lies Ahead

Ricci¹,

Pampaloni

Sommazzi

et al. 2021

Macromolecules

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“…Alkyllithium is a very reactive species commonly used in living anionic polymerizations as an initiator. A developed method to convert dialkylzinc to alkyllithium would be a powerful tool for the syntheses of various types of PO-based block copolymers (Scheme 1) [39]. Alkyllithium is a more reactive species than the corresponding dialkylzinc, and the reaction for converting alkyllithium to dialkylzinc is conventionally adopted, whereas its reverse reaction, i.e., converting dialkylzinc to alkyllithium is not favored and not yet realized.…”

Section: Converting Dialkylzinc To Alkyllithiummentioning

confidence: 99%

Polystyrene Chain Growth Initiated from Dialkylzinc for Synthesis of Polyolefin-Polystyrene Block Copolymers

et al. 2020

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Polyolefins (POs) are the most abundant polymers. However, synthesis of PO-based block copolymers has only rarely been achieved. We aimed to synthesize various PO-based block copolymers by coordinative chain transfer polymerization (CCTP) followed by anionic polymerization in one-pot via conversion of the CCTP product (polyolefinyl)2Zn to polyolefinyl-Li. The addition of 2 equiv t-BuLi to (1-octyl)2Zn (a model compound of (polyolefinyl)2Zn) and selective removal or decomposition of (tBu)2Zn by evacuation or heating at 130 °C afforded 1-octyl-Li. Attempts to convert (polyolefinyl)2Zn to polyolefinyl-Li were unsuccessful. However, polystyrene (PS) chains were efficiently grown from (polyolefinyl)2Zn; the addition of styrene monomers after treatment with t-BuLi and pentamethyldiethylenetriamine (PMDTA) in the presence of residual olefin monomers afforded PO-block-PSs. Organolithium species that might be generated in the pot of t-BuLi, PMDTA, and olefin monomers, i.e., [Me2NCH2CH2N(Me)CH2CH2N(Me)CH2Li, Me2NCH2CH2N(Me)Li·(PMDTA), pentylallyl-Li⋅(PMDTA)], as well as PhLi⋅(PMDTA), were screened as initiators to grow PS chains from (1-hexyl)2Zn, as well as from (polyolefinyl)2Zn. Pentylallyl-Li⋅(PMDTA) was the best initiator. The Mn values increased substantially after the styrene polymerization with some generation of homo-PSs (27–29%). The Mn values of the extracted homo-PS suggested that PS chains were grown mainly from polyolefinyl groups in [(polyolefinyl)2(pentylallyl)Zn]−[Li⋅(PMDTA)]+ formed by pentylallyl-Li⋅(PMDTA) acting onto (polyolefinyl)2Zn.

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“…Afterward, end-functionalized high trans-1,4-PM were prepared by means of Nd(BH 4 ) 3 with Mg n BuEt. [49] The living trans-1,4 stereoregular (> 97 %) polymer chain was reacted with benzophenone afforded trans-1,4-PM up to 83 % CPh 2 OH endgroup.…”

Section: Group 3 and Rare-earth Metalsmentioning

confidence: 99%

Stereoregular Polymerization of Acyclic Terpenes

2021

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The growing environmental pollution and the expected depleting of fossil resources have sparked interest in recent years for polymers obtained from monomers originating from renewable sources. Furthermore, nature can provide a variety of building blocks with special structural features (e. g. side groups or stereo-elements) that cannot be obtained so easily via fossilbased pathways. In this context, terpenes are widespread natural compounds coming from non-food crops, present in a large variety of structures, and ready to use as monomers with or without further modifications. The present review aims to provide an overview of how chemists can stereospecifically polymerize terpenes, particularly the acyclic ones like myrcene, ocimene, and farnesene, using different metal catalyst systems in coordination-insertion polymerization. Attention is also paid to their copolymers, which have recently been disclosed, and to the possible applications of these bio-based materials in various industrial sectors such as in the field of elastomers.

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Efficient One-Pot Synthesis of End-Functionalized trans-Stereoregular Polydiene Macromonomers

Cited by 32 publications

References 50 publications

Dienes Polymerization: Where We Are and What Lies Ahead

Dienes Polymerization: Where We Are and What Lies Ahead

Polystyrene Chain Growth Initiated from Dialkylzinc for Synthesis of Polyolefin-Polystyrene Block Copolymers

Stereoregular Polymerization of Acyclic Terpenes

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