Toward Olefin Multiblock Copolymers with Tailored Properties: A Molecular Perspective

Mohammadi, Yousef; Saeb, Mohammad Reza; Penlidis, Alexander; Jabbari, Esmaiel; Stadler, Florian J.; Zinck, Philippe; Vivaldo‐Lima, Eduardo

doi:10.1002/mats.202100003

Cited by 4 publications

(4 citation statements)

References 46 publications

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“…The simulation comprises microstructure details, molecular weight distributions and copolymer composition distributions. Recently, a hybrid programming between KMC and artificial neural network modeling has been reported to take advantage of both simulation techniques [14], and the connection between the reagent ratios, the topology and the property-related microstructural features was explored. Deterministic approaches have also been developed to study the CCTP processes.…”

Section: Introductionmentioning

confidence: 99%

Terpene Coordinative Chain Transfer Polymerization: Understanding the Process through Kinetic Modeling

Ubaldo-Alarcón¹,

Soriano‐Corral²,

Córdova³

et al. 2022

Polymers

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The interest in the Coordinative Chain Transfer Polymerization (CCTP) of a family of naturally occurring hydrocarbon monomers, namely terpenes, for the production of high-performance rubbers is increasing year by year. In this work, the synthesis of poly(β-myrcene) via CCTP is introduced, using neodymium versatate (NdV3), diisobutylaluminum hydrade (DIBAH) as the catalytic system and dimethyldichlorosilane (Me2SiCl2) as the activator. A bimodal distribution in the GPC signal reveals the presence of two populations at low conversions, attributable to dormants (arising from reversible chain transfer reactions) and dead chains (arising from termination and irreversible chain transfer reactions); a unimodal distribution is generated at medium and high conversions, corresponding to the dominant species, the dormant chains. Additionally, a mathematical kinetic model was developed based on the Method of Moments to study a set of selected experiments: ([β-myrcene]0:[NdV3]0:[DIBAH]0:[Me2SiCl2]0 = 660:1:2:1, 885:1:2:1, and 533:1:2:1). In order to estimate the kinetic rate constant of the systems, a minimization of the sum of squared errors (SSE) between the model predicted values and the experimental measurements was carried out, resulting in an excellent fit. A set of the Arrhenius parameters were estimated for the ratio [β-myrcene]0:[NdV3]0:[DIBAH]0:[Me2SiCl2]0 = 660:1:2:1 in a temperature range between 50 to 70 °C. While the end-group functionality (EGF) was predominantly preserved as the ratio [β-myrcene]0:[NdV3]0 was decreased, higher catalytic activity was obtained with a high ratio.

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Section: Introductionmentioning

confidence: 99%

Terpene Coordinative Chain Transfer Polymerization: Understanding the Process through Kinetic Modeling

Ubaldo-Alarcón¹,

Soriano‐Corral²,

Córdova³

et al. 2022

Polymers

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“…The KMC simulator provides a modest number of OBC structures that serves as database for the ANN, which can then produce e.g. a global mapping of OBC microstructures as a function of the input parameters (catalysts, monomers and CSA ratio). , These microstructures are mapped according to the soft and hard block length, composition, ethene sequence length, and the longest ethene sequence length. New OBC grades, i.e., microstructures that were not reached experimentally, were predicted using this tool.…”

Section: Coordinative Chain Transfer Polymerizationmentioning

confidence: 99%

Coordinative Chain Transfer and Chain Shuttling Polymerization

Mundil,

Bravo,

Merle

et al. 2023

Chem. Rev.

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Coordinative chain transfer polymerization, CCTP, is a degenerative chain transfer polymerization process that has a wide range of applications. It allows a highly controlled synthesis of polyolefins, stereoregular polydienes, and stereoregular polystyrene, including (stereo)block as well as statistical copolymers thereof. It also shows a green character by allowing catalyst economy during the synthesis of such polymers. CCTP notably allows the end functionalization of both the commodity and stereoregular specialty polymers aforementionned, control of the composition of statistical copolymers without adjusting the feed, and quantitative formation of 1-alkenes from ethene. A one-pot one-step synthesis of the original multiblock microstructures and architectures by chain shuttling polymerization (CSP) is also an asset of CCTP. This methodology takes advantage of the simultaneous presence of two catalysts of different selectivity toward comonomers that produce blocks of different composition/microstructure, while still allowing the chain transfer. This affords the production of highly performant functional polymers, such as thermoplastic elastomers and adhesives, among others. This approach has been extended to cyclic esters' and ethers' ring-opening polymerization, providing new types of multiblock microstructure. The present Review provides the state of the art in the field with a focus on the last 10 years.

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“…12 The invention of chain-shuttling polymerization technology 13 by Dow Chemical Company creates ethylene-octene multiblock copolymer with the popular name of olefin block copolymer (OBC) whose multiblock structure makes it have a low density, higher crystallization and melting temperature, better elastic recovery and wide applications. [14][15][16][17][18][19] However, the non-polar property of ethylene-based polyolefin elastomers is one of the biggest limitations to extending their applications. 20,21 Non-polar polyolefins can be modified to achieve polarity through proper chemical design and modifications.…”

Section: Introductionmentioning

confidence: 99%

“…Ethylene‐α olefin copolymers are important TPE species including ethylene‐octene random copolymer (POE) which is obtained by metallocene catalyzed copolymerization 9–11 and has a low melting point 12 . The invention of chain‐shuttling polymerization technology 13 by Dow Chemical Company creates ethylene‐octene multiblock copolymer with the popular name of olefin block copolymer (OBC) whose multiblock structure makes it have a low density, higher crystallization and melting temperature, better elastic recovery and wide applications 14–19 . However, the non‐polar property of ethylene‐based polyolefin elastomers is one of the biggest limitations to extending their applications 20,21 …”

Section: Introductionmentioning

confidence: 99%

Reactive melt‐grafting of maleic anhydride onto olefin block copolymer toward high‐performance polar polyolefin thermoplastic elastomer

Kou,

Ma,

et al. 2024

Polymer International

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The block structure of Olefin Block Copolymer (OBC) elastomer gives it good elasticity and heat‐resistance in relative to other polyolefin elastomers. However, the non‐polar nature of OBC chains limits its comprehensive properties like dyeing and toughening for polar engineering plastics. In this work, Maleic Anhydride (MA) and Dicumyl Peroxide (DCP) were selected as a typical polar monomer and a radical initiator to modify the polarity of OBC elastomer. During the melt‐grafting process, DCP content was tuned to optimize the grafting efficiency while the MA‐to‐OBC ratio was fixed as 5 wt%. It was found that all the melt‐grafting reactions show high‐efficiency and can be finished in 3 min at 170 °C. With the increase of DCP content, the estimated grafting degree of OBC‐g‐MA elastomer increases from 0.40% to 1.16% along with increased gel content from 4.27% to 22.44%. A suitable grafting process was obtained with DCP content of 3.0 wt% by balancing grafting efficiency and final mechanical properties. The optimized OBC‐g‐MA elastomer with grafting degree of 0.92% has a mechanical strength of 17.15 MPa, Young's modulus of 26.35 MPa, elongation of 1564%, and strain recovery of 59.73%. Additionally, contact angle test shows that polar grafting can increase surface hydrophilicity while excessive crosslinking promotes hydrophobicity. Therefore, our work has demonstrated the feasibility of reactive melt‐grafting method to prepare OBC‐g‐MA elastomer and can also provide processing reference for other chemical functionalization of polyolefin thermoplastic elastomers.This article is protected by copyright. All rights reserved.

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Toward Olefin Multiblock Copolymers with Tailored Properties: A Molecular Perspective

Abstract: Research data are not shared.

Cited by 4 publications

References 46 publications

Terpene Coordinative Chain Transfer Polymerization: Understanding the Process through Kinetic Modeling

Terpene Coordinative Chain Transfer Polymerization: Understanding the Process through Kinetic Modeling

Coordinative Chain Transfer and Chain Shuttling Polymerization

Reactive melt‐grafting of maleic anhydride onto olefin block copolymer toward high‐performance polar polyolefin thermoplastic elastomer

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