Cobalt catalysed controlled copolymerization: an efficient approach to bifunctional polyisoprene with enhanced properties

Gong, Dirong; Tang, Fawei; Xu, Yaqian; Hu, Zhonghan; Luo, Wanwei

doi:10.1039/d1py00101a

Cited by 21 publications

(41 citation statements)

References 60 publications

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“…However, this method poses critical challenges including loss of activity, poor control of the functional degree, and chain transfer and termination reactions associated with the detrimental effect of the functional group. 279 Mecking et al synthesized stereoregular trans-1,4-poly-(dienes) with three different types of functional groups by insertion polymerization. The functional groups were located simultaneously in the polymer backbone and at both chain ends, yielding heterotelechelic and in-chain-functionalized polymers.…”

Section: Stereoblock Diene Polymersmentioning

confidence: 99%

“…The functional copolymers show significantly improved hydrophilicity and good thermal properties useful for application in the rubber industry. 285…”

Section: Stereoblock Diene Polymersmentioning

confidence: 99%

“…The functional copolymers showed significantly improved hydrophilicity and good thermal properties. However, this method poses critical challenges including loss of activity, poor control of the functional degree, and chain transfer and termination reactions associated with the detrimental effect of the functional group …”

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%

“…The functional copolymers show significantly improved hydrophilicity and good thermal properties useful for application in the rubber industry. 285…”

Section: Stereoblock Diene Polymersmentioning

confidence: 99%

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

View full text Add to dashboard Cite

show abstract

“…Gong et al also reported on the synthesis of bifunctional monomers dienes derivatives (hydroxyl, furan and pyridine group) obtained from bio-sourced M and their controlled copolymerization with I via catalytic insertion mechanism. [67] A series of new Co-based complexes (51-55) (Figure 12) were tested, providing yields in most cases above 90 % in about 1 h. Copolymerization followed a first-order kinetics dependence on monomer without obvious chain transfer and termination. The role of the labile arm in inhibiting chain transfer reaction has also been hypothesized.…”

Section: Cobaltmentioning

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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“…Similar to polar polyolefin materials, functionalized Polymers 2021, 13, 3329 2 of 11 polydienes elastomers are also of great significance because the incorporated functional groups can greatly improve the compatibility between the polydienes matrix and reinforce polar fillers, such as carbon black, silica, etc., which therefore produces well-performing elastomers with good modulus, tensile strength, and other dynamic mechanical properties [13]. However, research n copolymerization with polar copolymers in this field o is very limited [14,15]. In the present research, a series copolymerizations of 1,3-butadiene with polar comonomer 2-(4-methoxyphenyl)-1,3-butadiene (2-MOPB) is conducted, and the corresponding catalytic performances and microstructures of the resulting copolymers are discussed.…”

Section: Introductionmentioning

confidence: 99%

cis-1,4 Selective Coordination Polymerization of 1,3-Butadiene and Copolymerization with Polar 2-(4-Methoxyphenyl)-1,3-butadiene by Acenaphthene-Based α-Diimine Cobalt Complexes Featuring Intra-Ligand π-π Stacking Interactions

et al. 2021

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Highly cis-1,4 selective (up to 98%) coordination–insertion polymerization of 1,3-butadiene (BD) has been achieved herein using acenaphthene-based α-diimine cobalt complexes. Due to the presence of intra-ligand π-π stacking interactions, the complexes revealed high thermostability, affording polybutadiene products in high yields. Moreover, all of the obtained polymers possessed a relatively narrow molecular weight distribution as well as high molecular weight (up to 92.2 × 104 Dalton). The molecular weights of the resultant polybutadienes could be finely tuned by varying polymerization parameters, including temperature, Al/Co ratio, etc. Moreover, the copolymerization of butadiene with polar monomer 2-(4-methoxyphenyl)-1,3-butadiene (2-MOPB) was also successfully realized to produce a type of polar cis-1,4 polybutadiene (cis-1,4 content: up to 98.1%) with a range of 2-MOPB content (0.46–1.83%). Water contact angle measurements indicated that the insertion of a polar monomer into a polymer chain could significantly improve the polymer’s surface property.

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Cobalt catalysed controlled copolymerization: an efficient approach to bifunctional polyisoprene with enhanced properties

Abstract: Preparation of functional polyisoprene via direct catalytic insertion polymerization has been preferred because the polymers’ regularity, molar mass and functionality can be facilely controlled by catalyst. However, this method has...

Cited by 21 publications

References 60 publications

Dienes Polymerization: Where We Are and What Lies Ahead

Dienes Polymerization: Where We Are and What Lies Ahead

Stereoregular Polymerization of Acyclic Terpenes

cis-1,4 Selective Coordination Polymerization of 1,3-Butadiene and Copolymerization with Polar 2-(4-Methoxyphenyl)-1,3-butadiene by Acenaphthene-Based α-Diimine Cobalt Complexes Featuring Intra-Ligand π-π Stacking Interactions

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