Polyolefin thermoplastic elastomers from 1-octene copolymerization with 1-decene and cyclopentene

Pierro, Ivana; Leone, Giuseppe; Zanchin, Giorgia; Canetti, Maurizio; Ricci, Giovanni; Bertini, Fabio

doi:10.1016/j.eurpolymj.2017.05.044

Cited by 29 publications

(19 citation statements)

References 65 publications

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“…The 1-octene and 1-decene polymers showed low-intensity scattering profiles, similar to those of 1-octene copolymers with low crystallinity previously reported. 22 The scattering profile of 1-octadecene polymers shows a discrete peak which is associated with the long period (L p ) that results from the electron density difference between crystalline and amorphous phases ( Figure 5C). The structural data together with the crystallinity and the melting temperature of the 1- octadecene polymers are consistent with a mixed morphology containing both bundled crystals and lamellar structures.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Chain-Walking Polymerization of α-Olefins by α-Diimine Ni(II) Complexes: Effect of Reducing the Steric Hindrance of Ortho- and Para-Aryl Substituents on the Catalytic Behavior, Monomer Enchainment, and Polymer Properties

et al. 2018

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With Brookhart type α-diimine Ni(II) based catalysts, it is highly challenging to tune polymers branching level and branch-type distribution, which in turn strongly affects thermal and mechanical properties, through the aryl ortho-positions modification, while maintaining high turnover frequencies (TOFs). Herein, we are interested in performing a systematic investigation on the polymerization of 1-octene, 1-decene, and 1-octadecene catalyzed by a series of α-diimine nickel(II) complexes with methyl ligand backbone and different substituents in aryl positions (Ni1−Ni6). In addition to bulky isopropyl and tert-butyl substituents described in the original Brookhart's work, complexes with different aryl ortho-and para-substituted α-diimine ligands, including the less sterically demanding methyl and ethyl substituents, are investigated. The 13 C NMR spectra of the polymers have been assigned in detail, and some unique features have been identified and related to the chain-walking coordination/insertion mechanism. Changes in the ligand structure and monomer size have important effects on the numerous combinations of insertion and chain-walking paths from which different branches are installed. We have also carried out a comprehensive investigation of the mechanical behavior of the polymers by means of uniaxial stretching until failure, step-cycle, and creep tensile tests. Overall, the resulting polymers exhibited a broad spectrum of tensile properties, depending on their microstructure and crystallinity which in turn are strongly affected by monomer length and type of α-diimine ligand. 1-Octene and 1-decene polymers behave as elastomers with excellent mechanical properties, i.e., high elongation at break (up to 2000%) and good strain recovery, while 1-octadecene polymers behave as plastomers.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Chain-Walking Polymerization of α-Olefins by α-Diimine Ni(II) Complexes: Effect of Reducing the Steric Hindrance of Ortho- and Para-Aryl Substituents on the Catalytic Behavior, Monomer Enchainment, and Polymer Properties

et al. 2018

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“…12,[35][36][37][38][39] Recently, α-diimine nickel catalyzed olefin polymerization using ethylene as sole feedstock has emerged as an appealing strategy for the synthesis of thermoplastic polyolefin elastomers. 30,31,[40][41][42][43][44][45][46][47] However, the reported nickel catalysts are almost insoluble in nonpolar alkane solvents and/or have poor thermal stability at high temperatures which are not qualified for industrial production. 24 Although the recently developed sterically very demanding 2,6-diarylmethyl nickel catalysts (Chart 2(B)) have excellent thermal stability, but the solubility of these catalysts in alkanes and even in toluene is still very poor due to the presence of a large number of rigid aromatic rings.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, α‐diimine nickel catalyzed olefin polymerization using ethylene as sole feedstock has emerged as an appealing strategy for the synthesis of thermoplastic polyolefin elastomers 30,31,40–47 . However, the reported nickel catalysts are almost insoluble in nonpolar alkane solvents and/or have poor thermal stability at high temperatures which are not qualified for industrial production 24 .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of polyethylene thermoplastic elastomer by using robust α‐diimine Ni(II) catalysts with abundant ^tBu substituents

Zhao

Dai

2021

Journal of Polymer Science

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The synthesis of polyethylene thermoplastic elastomers via α-diimine-nickelcatalyzed ethylene polymerization using polymerization conditions of elevated temperatures and alkane solvents is highly desirable in industrial production. In this contribution, we constructed a series of highly sterically demanding α-diimine Ni(II) catalysts with abundant t Bu substituents for this purpose. These nickel catalysts were examined for ethylene polymerization in hexanes at elevated temperatures (up to 90 C) and proved to be thermally robust at temperatures as high as 90 C. Generally, these nickel catalysts can generate highly branched (ca. 70-80/1000 C) polyethylenes with very high molecular weight (M n up to 55.79 × 10 4 g/mol) and the resultant polyethylenes displayed characteristics of thermoplastic elastomers with excellent elastic recovery (SR up to 84%). Compared with some similar α-diimine Ni(II) catalysts, it is shown that the presence of axial remote t Bu substituents not only facilitates the dissolution of the catalyst in alkanes, but also improves the elastic recovery value of the obtained polyethylene.

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“…Moreover, such developments have opened a new pathway toward production of linear polyethylene‐like structures using liquid olefinic monomers instead of ethylene . Thanks to the diversity of the catalytic structures, tunable polymer architectures from hyperbranched to linear are effectively synthesized using linear α‐olefins monomers . This way, polyethylene can be made in the liquid phase and under environmental pressure, without expensive handling equipment required for handling gaseous ethylene monomer.…”

Section: Introductionmentioning

confidence: 99%

A mechanistic study on the synthesis of branched functional polyethylene through reactive co‐polymer approach

Jandaghian

Ahmadjo

Mortzavi

et al. 2020

Applied Organom Chemis

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The reactive co‐polymer approach is one of the most promising techniques for the synthesis of functional polyolefins. Following this concept, 1‐hexene and p‐methylstyrene are co‐polymerized in the presence of a generic Brookhart‐type catalyst. The microstructures of the co‐polymers imply the tendency of p‐methylstyrene co‐monomers to place at the end of the structural branches formed by the chain walking reaction. The molar masses of the co‐polymers decrease, not only at higher levels of co‐monomer but surprisingly by decreasing reaction temperature. A mechanism consisting of a highly stable η3 metal–benzyl intermediate, which is quantitatively approved by density functional theory calculations, can delicately justify all the aforementioned observations. A series of the produced co‐polymers is selectively functionalized by maleic anhydride at the benzylic position of p‐methylstyrene, under very mild reaction conditions. Such a reactive intermediate opens the path for the introduction of different types of functionalities in polyolefins. Namely, the grafted co‐polymers were further functionalized by a triazole ring, which provides a transient supramolecular network through intermolecular hydrogen bonding.

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Polyolefin thermoplastic elastomers from 1-octene copolymerization with 1-decene and cyclopentene

Cited by 29 publications

References 65 publications

Chain-Walking Polymerization of α-Olefins by α-Diimine Ni(II) Complexes: Effect of Reducing the Steric Hindrance of Ortho- and Para-Aryl Substituents on the Catalytic Behavior, Monomer Enchainment, and Polymer Properties

Chain-Walking Polymerization of α-Olefins by α-Diimine Ni(II) Complexes: Effect of Reducing the Steric Hindrance of Ortho- and Para-Aryl Substituents on the Catalytic Behavior, Monomer Enchainment, and Polymer Properties

Synthesis of polyethylene thermoplastic elastomer by using robust α‐diimine Ni(II) catalysts with abundant ^tBu substituents

A mechanistic study on the synthesis of branched functional polyethylene through reactive co‐polymer approach

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Polyolefin thermoplastic elastomers from 1-octene copolymerization with 1-decene and cyclopentene

Cited by 29 publications

References 65 publications

Chain-Walking Polymerization of α-Olefins by α-Diimine Ni(II) Complexes: Effect of Reducing the Steric Hindrance of Ortho- and Para-Aryl Substituents on the Catalytic Behavior, Monomer Enchainment, and Polymer Properties

Chain-Walking Polymerization of α-Olefins by α-Diimine Ni(II) Complexes: Effect of Reducing the Steric Hindrance of Ortho- and Para-Aryl Substituents on the Catalytic Behavior, Monomer Enchainment, and Polymer Properties

Synthesis of polyethylene thermoplastic elastomer by using robust α‐diimine Ni(II) catalysts with abundant tBu substituents

A mechanistic study on the synthesis of branched functional polyethylene through reactive co‐polymer approach

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Synthesis of polyethylene thermoplastic elastomer by using robust α‐diimine Ni(II) catalysts with abundant ^tBu substituents