Halide-free neodymium phosphate based catalyst for highly <i>cis</i>-1,4 selective polymerization of dienes

Ren, Yixin; Miller, Justin T.; Polderman, Stefanie T.; Vo, Trinh D.; Wallace, Adele C.; Cue, John Michael O.; Tran, Sarah T.; Stefan, Mihaela C.

doi:10.1039/c8ra10050k

Cited by 9 publications

(8 citation statements)

References 27 publications

(36 reference statements)

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“…A halide-free complex, in which Nd is coordinated with three bidentate diethylphosphate (DEP) ligands ([Nd(μ-DEP) 3 ] x and combined with Al i Bu 3 , was reported by Stefan et al to promote M polymerization at room temperature. [55] High cis-1,4 selectivity (� 95 %), M n = 13-48.5 kg mol À 1 , and relatively narrow Ð (1.8) were detected. Kinetics experiments demonstrated pseudo-living character of polymerization, confirmed by the successful synthesis, through sequential monomer addition, of block copolymer poly(M-b-I) (M n = 15.5 kg mol À 1 , Ð = 3.1).…”

Section: Group 3 and Rare-earth Metalsmentioning

confidence: 96%

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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Section: Group 3 and Rare-earth Metalsmentioning

confidence: 96%

Stereoregular Polymerization of Acyclic Terpenes

2021

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“…In addition, the system had the ability to produce poly(myrcene‐ b‐ isoprene) and poly(myrcene‐ b‐ methyl methacrylate) block copolymers by adding monomers in sequence. Later on, the same group [29] reported that halide‐free neodymium diethyl phosphate complex combined with TIBA promoted the polymerization of Myr to afford polymers with relatively narrow molecular weight distribution ( M w / M n =1.8), moderate molecular weight ( M n =13000 g/mol) and comparatively high cis ‐1,4 selectivity up to 96% (Figure 5). The system also produced block copolymer poly(myrcene‐ b‐ isoprene), containing the composition of 25 mol% of poly( β ‐myrcene) sequence and 75 mol% of poly(isoprene) sequence.…”

Section: Bio‐based Linear Terpenes As Conjugated Dienes For Rare‐eart...mentioning

confidence: 99%

Section: Bio‐based Linear Terpenes As Conjugated Dienes For Rare‐eart...mentioning

confidence: 99%

Polymerization of Bio‐Derived Conjugated Dienes with Rare‐Earth‐Metal Complexes

You

Shi

Yan

et al. 2022

Chemistry An Asian Journal

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The reliance of both our life and industry on fossil resource and the alarming accumulation of polymeric materials in the environment have presented huge challenges to sustainable society. Nowadays, utilization of renewable monomers as building blocks for polymeric materials has emerged as a hot topic and increasingly gained attention from chemists. As a class of biomass with abundance and low cost, terpenes are typical hydrocarbon‐rich natural compounds, and some of them, such as myrcene and farnesene, are inherently suitable for coordination polymerization. In this review, we focus on the rare‐earth metal catalyzed highly regio‐ and stereoselective polymerization of bio‐based conjugated dienes, especially the ones from terpene‐derived compounds with or without modifications. This review also discusses the future direction on the modification of these bio‐based conjugated dienes.

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“…This type of catalyst is highly active and leads to stereoregular polymers with high content of the 1,4- cis microstructure, which is needed for adequate elasticity, high fatigue and crack resistance, and low heat buildup in synthetic rubber. Vulcanized products obtain better mechanical properties (300% modulus, tensile strength, and elongation at breakage) with the content of the 1,4- cis microstructure [ 20 ]. The vulcanization of PM and PF was compared with PB and PI, using the same vulcanization process parameters and with/without carbon black, to elucidate the influence of the chemical structure on the crosslinking network and mechanical properties compared to conventional petroleum-based rubbers.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Vulcanization of Polymyrcene and Polyfarnesene Bio-Based Rubbers: Influence of the Chemical Structure over the Vulcanization Process and Mechanical Properties

et al. 2022

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The overuse of fossil-based resources to produce thermoplastic materials and rubbers is dramatically affecting the environment, reflected in its clearest way as global warming. As a way of reducing this, multiple efforts are being undertaken including the use of more sustainable alternatives, for instance, those of natural origin as the main feedstock alternative, therefore having a lower carbon footprint. Contributing to this goal, the synthesis of bio-based rubbers based on β-myrcene and trans-β-farnesene was addressed in this work. Polymyrcene (PM) and polyfarnesene (PF) were synthesized via coordination polymerization using a neodymium-based catalytic system, and their properties were compared to the conventional polybutadiene (PB) and polyisoprene (PI) also obtained via coordination polymerization. Moreover, different average molecular weights were also tested to elucidate the influence over the materials’ properties. The crosslinking of the rubbers was carried out via conventional and efficient vulcanization routes, comparing the final properties of the crosslinking network of bio-based PM and PF with the conventional fossil-based PB and PI. Though the mechanical properties of the crosslinked rubbers improved as a function of molecular weight, the chemical structure of PM and PF (with 2 and 3 unsaturated double bonds, respectively) produced a crosslinking network with lower mechanical properties than those obtained by PB and PI (with 1 unsaturated double bond). The current work contributes to the understanding of improvements (in terms of crosslinking parameters) that are required to produce competitive rubber with good sustainability/performance balance.

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Halide-free neodymium phosphate based catalyst for highly cis-1,4 selective polymerization of dienes

Abstract: [Nd(μ-DEP)3]x/TIBA stereospecifically polymerizes myrcene in a pseudo-living Ziegler–Natta like catalytic system despite the absence of a halide.

Cited by 9 publications

References 27 publications

Stereoregular Polymerization of Acyclic Terpenes

Stereoregular Polymerization of Acyclic Terpenes

Polymerization of Bio‐Derived Conjugated Dienes with Rare‐Earth‐Metal Complexes

Synthesis and Vulcanization of Polymyrcene and Polyfarnesene Bio-Based Rubbers: Influence of the Chemical Structure over the Vulcanization Process and Mechanical Properties

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