Chemo‐ and stereoselective polymerization of 3‐methylenehepta‐1,6‐Diene and Its thiol‐ene modification

Li, Lei; Li, Shihui; Cui, Dongmei

doi:10.1002/pola.28463

Cited by 10 publications

(9 citation statements)

References 56 publications

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“…Thiol–ene click chemistry − was employed to modify v-POEs for introducing dihydroxyl groups. In typical 1 H NMR spectra of v-POE2 and h-POE2, proton signals at 4.8–6.0 ppm are attributed to the vinyl of v-POE2, and signals at 3.5–3.9 ppm are derived from the methylene and methine protons adjacent to dihydroxyl groups of h-POE2 (Figure b).…”

Section: Results and Discussionmentioning

confidence: 99%

“…Vinyl-functionalized POEs (v-POEs) are first synthesized using a constrained geometry catalyst ([Me 2 Si(N t Bu)(Me 4 Cp)]TiCl 2 , CGC) and methylaluminoxane (MAO) at 110 °C . The pendant vinyl groups of v-POEs are modified to dihydroxyl groups with thermal- or photoinitiated thiol–ene click chemistry. − The resulted hydroxyl-functionalized POEs (h-POEs) are further cross-linked with bis-dioxaborolane via melt extrusion to form boronic ester cross-linked POEs (BPOEs).…”

Section: Introductionmentioning

confidence: 99%

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Dynamically Cross-Linked Polyolefin Elastomers with Highly Improved Mechanical and Thermal Performance

et al. 2021

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The controllable introduction of dynamical chemical cross-linking into polymers permits the development of recyclable polymer products with high performance. However, challenges lie in chemically inert polyolefins, which are the largest polymer product in the world to date. Here, we demonstrate the preparation of polyolefin elastomers (POEs) with tunable dynamic chemical cross-linking, compatible with their industrial production. Boronic ester bond cross-linked POEs (BPOEs) present high mechanical performances with tensile strength (σ) up to 23.8 MPa, Young's modulus (E) up to 29.0 MPa, and toughness (U T ) up to 69.6 MJ•m −3 , far superior to those reported elastomers. BPOEs also demonstrate good thermal stability maintaining a steady storage modulus plateau of 2.9 MPa above 100 °C, instead of 0.2 MPa for pristine POEs. After reprocessing three times, BPOEs show a good reprocessability with a σ recovery of 85.6%, an E of 108.5%, a U T of 95.7%, and an elongation at break (ε) of 97.1%, even higher than that of commercial POEs such as POE-8150 of Dow Company. Our method thus permits the future development of higher-performance POEs and other polyolefins with good reprocessability and recyclability.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dynamically Cross-Linked Polyolefin Elastomers with Highly Improved Mechanical and Thermal Performance

et al. 2021

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“…Lately, further work on the synthesis of random copolymers of 3-methylenehepta-1,6-diene (MHD) with I or M, using the ternary catalytic system 31/[Ph 3 C][B(C 6 F 5 ) 4 ]/Al i Bu 3 (6 h, À 30 °C, chlorobenzene) was carried out. [59] The resulting copolymers had high regio and stereoselectivities (1,2-selectivity > 99 %, mm triad > 90 %), as confirmed by NMR spectroscopy. Molecular weights were rather low (M n = 9-13 kg mol À 1 ) with narrow Ð (1.5-1.6).…”

Section: Group 3 and Rare-earth Metalsmentioning

confidence: 72%

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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“…Postpolymerization modification of polymers bearing pendant reactive side groups is a powerful synthetic strategy to access functional materials. − However, cumbersome protection/deprotection processes , might be required when functional groups are incompatible with polymerization methods, decreasing significantly synthetic efficiency. Polymerization of divinyl monomers is a straightforward alternative as resultant polymers bearing the readily reactive CC groups attaching to the main chain .…”

Section: Introductionmentioning

confidence: 99%

Chemo- and Stereoselective Polymerization of Polar Divinyl Monomers by Rare-Earth Complexes

Liu

Zhao

et al. 2021

Macromolecules

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Chemoselective polymerization of divinyl monomers is a promising strategy to access functional polymers via postpolymerization, which however, encounters a cross-linking problem. Herein, we report the coordination polymerization of polar divinyl styrenyl monomers 1-(allyloxy)-4-vinylbenzene (AOS), 1-(but-3-en-1-yloxy)-4-vinylbenzene (BOS), 1-(pent-4-en-1-yloxy)-4-vinylbenzene (POS), and 1-(hex-5-en-1-yloxy)-4-vinylbenzene (HOS) by employing the thiophene-fused cyclopentadienyl scandium bis(alkyl) complexes (2,5-Me2-3-Ph-6H-cyclopenta[b]thiophenyl)Sc(CH2SiMe3)2THF (1) and (2,4,5,6-Me4-4H-cyclopenta[b]thiophenyl)Sc(CH2SiMe3)2THF (2) and the pyridinyl methylene fluorenyl rare-earth metal complexes (Py-CH2-Flu)Sc(CH2SiMe3)2 (3) and (Py-CH2-Flu)Y(CH2SiMe3)2THF (4). Complexes 1 and 2 show high chemoselectivity for these polar divinyl styrenyl monomers across the styrenyl CC bond but give atactic products. Catalysts 3 and 4 exhibit solitary chemoselectivity to give atactic poly(AOS) but syndiotactic poly(BOS), poly(POS), and poly(HOS). The copolymerization of the polar divinyl styrenyl monomers with ethylene (E) mediated by 3 exhibits chemoselectivity to afford POS/E and HOS/E copolymers but homopolymer poly(AOS). The reasons behind the (co)polymerization behaviors were investigated by DFT calculation.

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Chemo‐ and stereoselective polymerization of 3‐methylenehepta‐1,6‐Diene and Its thiol‐ene modification

Cited by 10 publications

References 56 publications

Dynamically Cross-Linked Polyolefin Elastomers with Highly Improved Mechanical and Thermal Performance

Dynamically Cross-Linked Polyolefin Elastomers with Highly Improved Mechanical and Thermal Performance

Stereoregular Polymerization of Acyclic Terpenes

Chemo- and Stereoselective Polymerization of Polar Divinyl Monomers by Rare-Earth Complexes

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