Balance of the steric hindrance and solubility of alkoxy ligands for ultrahigh-activity molybdenum-based butadiene coordination polymerization

Xie, Tinghao; Tang, Jian; Geng, Jieting; Wang, Xiaotong; Hua, Jing

doi:10.1039/d1py01402a

Cited by 8 publications

(7 citation statements)

References 29 publications

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“…To obtain mechanically robust networks, atactic 1,2-PB with M n of 455 kDa and 1,2-content of 72% was selected. The 1,2-PB was prepared by molybdenum-based catalyst-catalyzed polymerization . The abundant vinyl side groups on 1,2-PB molecular chains provide vast opportunities for postfunctionalization.…”

Section: Resultsmentioning

confidence: 99%

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Tough and Recyclable Polybutadiene Elastomer Based on Quadruple Hydrogen Bonding

Kang

Wang

et al. 2023

ACS Appl. Polym. Mater.

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The commercially available 1,2-polybutadiene (1,2-PB) contains highly reactive CC bonds and has excellent machinability, which is an ideal raw material for preparing thermoplastic elastomers. The preparation of supramolecular cross-linked 1,2-PB thermoplastic elastomer with good recyclability and excellent mechanical properties has promising applications. Here, the 1,2-PB elastomers (UPB elastomers) were prepared by conjugating a few percent 2-ureido-4[1H]-pyrimidinone (UPy) self-complementary quadruple hydrogen bonding units onto the high molecular weight (M n) 1,2-PB chains via the thiol-ene click reaction. The used 2-(mercaptoethyl-ureido)-pyrimidinone derivative (UPy-SH) with a branched alkyl group had good compatibility with 1,2-PB in organic solvent contributing to a high transparency of recyclable UPB elastomers. The cross-linking density of UPB elastomers can be conveniently adjusted by varying the UPy content, which ultimately determined the mechanical properties of resulting supramolecular elastomers. Abundant chain entanglements formed by 1,2-PB chains with a high M n of 455 kDa and strong quadruple hydrogen bonding networks formed by side UPy units endowed UPB elastomers with excellent mechanical properties and damping properties. It was found that sample UPB-2 containing 2 mol % UPy units showed a tensile strength of 13.4 MPa, a high elongation at break of 1167%, a high elastic recovery of 89% (under large tensile deformation of 400%), a high peak tan δ value (tan δmax) of 1.4, and an effective damping temperature range width of 30.6 °C. Moreover, UPB elastomers have good recyclability given the noncovalent cross-linking networks. This effective and universal strategy provides some insights into the design of physically cross-linked high-performance 1,2-polybutadiene elastomers.

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Section: Resultsmentioning

confidence: 99%

“…The 1,2-PB was prepared by molybdenum-based catalyst-catalyzed polymerization. 34 The abundant vinyl side groups on 1,2-PB molecular chains provide vast opportunities for postfunctionalization. Here, the highly efficient and selective thiol-ene click reaction was adopted to prepare UPy functionalized 1,2-PB.…”

Section: Preparation Of Upb Elastomersmentioning

confidence: 99%

Tough and Recyclable Polybutadiene Elastomer Based on Quadruple Hydrogen Bonding

Kang

Wang

et al. 2023

ACS Appl. Polym. Mater.

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“…[5][6][7] Ziegler-Natta catalysts based on transition metal compounds, such as Ti, V, Cr, Mo, Fe, Co, and Ni, have emerged successively, and they can be used to synthesize polybutadiene with controllable microstructures. 2,[8][9][10][11][12][13] Afterward, with the discovery of methylaluminoxane (MAO), various transition metal-based metallocene and non-metallocene catalysts with well-defined chemical structures have been investigated. Many complexes based on Ti, [14][15][16] Sc, [17][18][19][20] Y, [21][22][23] Cr, 24,25 V, [26][27][28] Co, 29,30 Fe, [31][32][33] etc.…”

Section: Introductionmentioning

confidence: 99%

Pyridine-amido aluminum catalyst precursors for 1,3-butadiene transition-metal-free stereospecific polymerization

et al. 2023

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“…Compared with the common rubber materials such as natural rubber, and styrene‐butadiene rubber, 1,2‐polybutadiene (1,2‐PB) features excellent aging resistance 4 . Furthermore, 1,2‐PB exhibits excellent wet skid resistance and low heat build‐up properties 5,6 . Aging is a process in which the properties of rubber materials gradually deteriorate under the action of high temperature, 7 oxygen, 8 oil, acids, and other active chemicals 9,10 .…”

Section: Introductionmentioning

confidence: 99%

“…4 Furthermore, 1,2-PB exhibits excellent wet skid resistance and low heat build-up properties. 5,6 Aging is a process in which the properties of rubber materials gradually deteriorate under the action of high temperature, 7 oxygen, 8 oil, acids, and other active chemicals. 9,10 As we all know, oxidative aging is one of the most common types, and it is essential to preventing the thermal oxygen aging of rubber.…”

Section: Introductionmentioning

confidence: 99%

Balancing anti‐migration and anti‐aging behavior of binary antioxidants for high‐performance 1,2‐polybutadiene rubber

Han

Geng

Wang

et al. 2022

Polymers for Advanced Techs

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For rubber materials, the antioxidants are significant for maintaining the long service life when suffering from external stimuli. However, the common low-molecularweight antioxidants easily migrate to the rubber surface and lose the anti-aging effect. In this work, we develop highly anti-migration hindered phenolic antioxidants, which have been obtained by covalently grafting 3,5-di-tert-butyl-4-hydroxybenzoic acid (AO) onto carbon nanotubes (CNTs). To improve the adhesion of AO and CNTs, the polydopamine with the potential reactive functional groups was linked between antioxidants and CNTs by mussel biomimetic strategy. The binary antioxidants integrated the good reinforcement and dispersity of CNTs with the anti-aging characteristics of hindered phenol. What is more, the experimental results indicate that the total loading efficiency of AO could reach 11.7 wt%. The 1,2-Polybutadiene/CNTs-AO composites could be stored in a thermal oxidation environment for 15 days with minimal degradation of mechanical properties. This strategy proposed herein provides insights into the development of highly anti-migration and anti-aging antioxidants by a simple, cost-effective, and pollution-free method.

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Balance of the steric hindrance and solubility of alkoxy ligands for ultrahigh-activity molybdenum-based butadiene coordination polymerization

Abstract: Multiple chlorine atoms are replaced by low alkoxy blocking ligands, so that the molybdenum-based catalyst is evenly dispersed, and the polymerization activity is increased while ensuring stable 1,2-selectivity.

Cited by 8 publications

References 29 publications

Tough and Recyclable Polybutadiene Elastomer Based on Quadruple Hydrogen Bonding

Tough and Recyclable Polybutadiene Elastomer Based on Quadruple Hydrogen Bonding

Pyridine-amido aluminum catalyst precursors for 1,3-butadiene transition-metal-free stereospecific polymerization

Balancing anti‐migration and anti‐aging behavior of binary antioxidants for high‐performance 1,2‐polybutadiene rubber

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