Controlled Copolymerization of Ethylene and Biosourced Comonomers Using Dibenzobarrelene-Based <i>α</i>-Diimine Nickel Catalyst

<b>The</b> development of earth-abundant nickel-based catalysts is currently one of the greatest challenges for the straightforward synthesis of functionalized polyolefins. With environmental protection concerns, controllable copolymerizations of ethylene with biosourced comonomers deriv...

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Main Authors: Handou Zheng, Junsong Wang, Zonglin Qiu, Chunyu Feng, Haotian Zhou, Guangshui Tu, Haiyang Gao
Format: Article
Language:English
Published: MDPI AG 2025-05-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/11/2402
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author Handou Zheng
Junsong Wang
Zonglin Qiu
Chunyu Feng
Haotian Zhou
Guangshui Tu
Haiyang Gao
author_facet Handou Zheng
Junsong Wang
Zonglin Qiu
Chunyu Feng
Haotian Zhou
Guangshui Tu
Haiyang Gao
author_sort Handou Zheng
collection DOAJ
description <b>The</b> development of earth-abundant nickel-based catalysts is currently one of the greatest challenges for the straightforward synthesis of functionalized polyolefins. With environmental protection concerns, controllable copolymerizations of ethylene with biosourced comonomers derived from castor oil, such as methyl 10-undecenoate (U-COOMe), 10-undecen-1-ol (U-OH), or 10-undecenyl bromide (U-Br), were realized using <i>α</i>-diimine nickel catalyst (<b>Ni-DBB</b>) with dibenzobarrelene backbone. Catalyst <b>Ni-DBB</b> was highly tolerant toward polar comonomers, and functional polyethylenes were successfully prepared. The influences of the polar group, temperature, and comonomer concentration were studied in detail. Catalyst <b>Ni-DBB</b> was able to catalyze the copolymerization of ethylene with U-OH to afford high-molecular-weight (~180 kg/mol) functional polyethylene in a controlled fashion. NMR analysis showed that the produced functional polyethylenes were highly branched and had broad melting peaks ranging from 0 to 30 °C. Water contact angle (WCA) measurements showed that the surface of the obtained hydroxyl-functionalized polyethylene changed from hydrophobic to hydrophilic with the introduction of the comonomer U-OH.
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spelling doaj-art-50df84f4d6a2476cb9c481f9c57bcd142025-08-20T02:33:06ZengMDPI AGMolecules1420-30492025-05-013011240210.3390/molecules30112402Controlled Copolymerization of Ethylene and Biosourced Comonomers Using Dibenzobarrelene-Based <i>α</i>-Diimine Nickel CatalystHandou Zheng0Junsong Wang1Zonglin Qiu2Chunyu Feng3Haotian Zhou4Guangshui Tu5Haiyang Gao6School of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou 510275, ChinaSchool of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou 510275, ChinaSchool of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou 510275, ChinaSchool of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou 510275, ChinaSchool of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou 510275, ChinaSchool of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou 510275, ChinaSchool of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou 510275, China<b>The</b> development of earth-abundant nickel-based catalysts is currently one of the greatest challenges for the straightforward synthesis of functionalized polyolefins. With environmental protection concerns, controllable copolymerizations of ethylene with biosourced comonomers derived from castor oil, such as methyl 10-undecenoate (U-COOMe), 10-undecen-1-ol (U-OH), or 10-undecenyl bromide (U-Br), were realized using <i>α</i>-diimine nickel catalyst (<b>Ni-DBB</b>) with dibenzobarrelene backbone. Catalyst <b>Ni-DBB</b> was highly tolerant toward polar comonomers, and functional polyethylenes were successfully prepared. The influences of the polar group, temperature, and comonomer concentration were studied in detail. Catalyst <b>Ni-DBB</b> was able to catalyze the copolymerization of ethylene with U-OH to afford high-molecular-weight (~180 kg/mol) functional polyethylene in a controlled fashion. NMR analysis showed that the produced functional polyethylenes were highly branched and had broad melting peaks ranging from 0 to 30 °C. Water contact angle (WCA) measurements showed that the surface of the obtained hydroxyl-functionalized polyethylene changed from hydrophobic to hydrophilic with the introduction of the comonomer U-OH.https://www.mdpi.com/1420-3049/30/11/2402<i>α</i>-diimine nickelcopolymerizationbiosourced monomersfunctional polyethylene
spellingShingle Handou Zheng
Junsong Wang
Zonglin Qiu
Chunyu Feng
Haotian Zhou
Guangshui Tu
Haiyang Gao
Controlled Copolymerization of Ethylene and Biosourced Comonomers Using Dibenzobarrelene-Based <i>α</i>-Diimine Nickel Catalyst
Molecules
<i>α</i>-diimine nickel
copolymerization
biosourced monomers
functional polyethylene
title Controlled Copolymerization of Ethylene and Biosourced Comonomers Using Dibenzobarrelene-Based <i>α</i>-Diimine Nickel Catalyst
title_full Controlled Copolymerization of Ethylene and Biosourced Comonomers Using Dibenzobarrelene-Based <i>α</i>-Diimine Nickel Catalyst
title_fullStr Controlled Copolymerization of Ethylene and Biosourced Comonomers Using Dibenzobarrelene-Based <i>α</i>-Diimine Nickel Catalyst
title_full_unstemmed Controlled Copolymerization of Ethylene and Biosourced Comonomers Using Dibenzobarrelene-Based <i>α</i>-Diimine Nickel Catalyst
title_short Controlled Copolymerization of Ethylene and Biosourced Comonomers Using Dibenzobarrelene-Based <i>α</i>-Diimine Nickel Catalyst
title_sort controlled copolymerization of ethylene and biosourced comonomers using dibenzobarrelene based i α i diimine nickel catalyst
topic <i>α</i>-diimine nickel
copolymerization
biosourced monomers
functional polyethylene
url https://www.mdpi.com/1420-3049/30/11/2402
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