Multi-walled Carbon Nanotubes as a Ligand in Nickel -Diimine Based Ethylene Polymerization

Citation: Sasan Talebnezhad, Saeed Pourmahdian. Multi-walled Carbon Nanotubes as a Ligand in Nickel -Diimine Based Ethylene Polymerization[J]. Chinese Journal of Polymer Science, 2015, 33(10): 1389-1403. doi: 10.1007/s10118-015-1696-x shu

Multi-walled Carbon Nanotubes as a Ligand in Nickel -Diimine Based Ethylene Polymerization

Sasan Talebnezhad ^1, ,
Saeed Pourmahdian ^{1,
,}

1.
Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran 15914, Iran

通讯作者: Saeed Pourmahdian,

摘要: Two novel heterogeneous nickel -diimine based polymerization catalysts, containing MWCNT as the main ligand, were synthesized by novel in situ catalyst preparation technique. The in situ synthesis was performed by covalent attachment of the acenaphthenic ligand core to amine functionalized MWCNT ligand arms through diimine bonding and further nickel dibromide chelation. The prepared catalysts were fully characterized and their structures and supporting efficiencies were determined. Single or double introduction of the MWCNTs through their ends or sidewall(s) in the catalytic system, as a ligand, influenced the catalytic performance, microstructure and morphology of obtained polyethylenes. MWCNT sidewall bonding to para-aryl position of the tetramethylphenyl moiety performed as more electron-donating ligand than MWCNT ends linked to the imine bond and protected the catalytic system to retain its activity. This character resulted in the maintenance of the resulting polymer topology at elevated temperatures so that the catalytic activity and the obtained polymer melting points remained around 110 g PEmmol-1 Nih-1 and 123 ℃ in all polymerization temperatures respectively. In polymerization trials, molecular weight fall against temperature was not as sharp as what had been observed in sequentially prepared catalysts insofar as the molecular weight of resultant polymer at 60 ℃ reached to 310000 gmol-1 which was close to the highest value had been reported at 30 ℃ for sequentially prepared catalysts. TEM observations showed the presence of the stopped-growth polymer chains due to geometrical constrains or ligand debonding for both catalytic systems.

关键词:

English

Multi-walled Carbon Nanotubes as a Ligand in Nickel -Diimine Based Ethylene Polymerization

Sasan Talebnezhad ^1, ,
Saeed Pourmahdian ^{1,
,}

1.
Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran 15914, Iran

Corresponding author: Saeed Pourmahdian,

Received Date: 17 March 2015
Revised Date: 19 April 2015
Available Online: 05 October 2015

Abstract: Two novel heterogeneous nickel -diimine based polymerization catalysts, containing MWCNT as the main ligand, were synthesized by novel in situ catalyst preparation technique. The in situ synthesis was performed by covalent attachment of the acenaphthenic ligand core to amine functionalized MWCNT ligand arms through diimine bonding and further nickel dibromide chelation. The prepared catalysts were fully characterized and their structures and supporting efficiencies were determined. Single or double introduction of the MWCNTs through their ends or sidewall(s) in the catalytic system, as a ligand, influenced the catalytic performance, microstructure and morphology of obtained polyethylenes. MWCNT sidewall bonding to para-aryl position of the tetramethylphenyl moiety performed as more electron-donating ligand than MWCNT ends linked to the imine bond and protected the catalytic system to retain its activity. This character resulted in the maintenance of the resulting polymer topology at elevated temperatures so that the catalytic activity and the obtained polymer melting points remained around 110 g PEmmol-1 Nih-1 and 123 ℃ in all polymerization temperatures respectively. In polymerization trials, molecular weight fall against temperature was not as sharp as what had been observed in sequentially prepared catalysts insofar as the molecular weight of resultant polymer at 60 ℃ reached to 310000 gmol-1 which was close to the highest value had been reported at 30 ℃ for sequentially prepared catalysts. TEM observations showed the presence of the stopped-growth polymer chains due to geometrical constrains or ligand debonding for both catalytic systems.

Key words:

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Multi-walled Carbon Nanotubes as a Ligand in Nickel -Diimine Based Ethylene Polymerization

通讯作者: Saeed Pourmahdian,

English

Multi-walled Carbon Nanotubes as a Ligand in Nickel -Diimine Based Ethylene Polymerization

Corresponding author: Saeed Pourmahdian,

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Multi-walled Carbon Nanotubes as a Ligand in Nickel -Diimine Based Ethylene Polymerization

通讯作者: Saeed Pourmahdian,

English

Multi-walled Carbon Nanotubes as a Ligand in Nickel -Diimine Based Ethylene Polymerization

Corresponding author: Saeed Pourmahdian,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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