Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems

Feng Wang; Heng Liu; Wenjie Zheng; Jun Guo; Chunyu Zhang; Liping Zhao; Hexin Zhang; Yanming Hu; Chenxi Bai; Xuequan Zhang

doi:10.1016/j.polymer.2013.10.031

Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems

Feng Wang, Heng Liu, Wenjie Zheng, Jun Guo, Chunyu Zhang, Liping Zhao, Hexin Zhang, Yanming Hu, Chenxi Bai, Xuequan Zhang

Chemical Engineering and Materials Science

Research output: Contribution to journal › Article › peer-review

36 Scopus citations

Abstract

Coordinative chain transfer polymerization (CCTP) of 1,3-butadiene was assessed by employing several traditional Ziegler-Natta type Nd-based catalytic systems. Both the types of alkylaluminum as CTA and chloride donor as third component significantly affected the chain transfer characteristic of the CCTP systems. Among the catalytic systems examined, Nd(OiPr)₃/Al(iBu) ₂H/Me₂SiCl₂ and Nd(OiPr)₃/Al(iBu) ₂H/Al₂Et₃Cl₃ systems exhibited the highest catalytic efficiency, yielding 6-10 polymer chains per Nd atom in the presence of 20 equiv. CTA. Kinetic examination revealed that Nd(OiPr) ₃/Al(iBu)₂H/Me₂SiCl₂ and Nd(OiPr)₃/Al(iBu)₂H/Al₂Et₃Cl ₃ catalytic systems proceeded with fully- and semi-reversible chain transfer reactions, respectively. Quantitative formation of polymers was observed in each step of the 1,3-butadiene seeding polymerization, indicating the living mode of the two catalytic systems. Moreover, the triblock copolymers, PBD-b-PIP-b-PBD and PBD-b-PIP-b-PCL, were successfully synthesized with Nd(OiPr)₃/Al(iBu)₂H/Me₂SiCl₂ catalytic system.

Original language	English (US)
Pages (from-to)	6716-6724
Number of pages	9
Journal	Polymer
Volume	54
Issue number	25
DOIs	https://doi.org/10.1016/j.polymer.2013.10.031
State	Published - Nov 27 2013

Bibliographical note

Funding Information:
The authors appreciate financial supports from the National Science and Technology Infrastructure Program ( 2007BAE14 B01-06 ), The Fund for National Natural Scientific Foundation of China (No. 20974016 and No. 51203147 ), The Jilin Provincial Research Fund for Basic Research, China (No. 20130102007JC ).

Keywords

1,3-Butadiene
Coordinative chain transfer polymerization
Neodymium-based catalyst

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title = "Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems",

abstract = "Coordinative chain transfer polymerization (CCTP) of 1,3-butadiene was assessed by employing several traditional Ziegler-Natta type Nd-based catalytic systems. Both the types of alkylaluminum as CTA and chloride donor as third component significantly affected the chain transfer characteristic of the CCTP systems. Among the catalytic systems examined, Nd(OiPr)3/Al(iBu) 2H/Me2SiCl2 and Nd(OiPr)3/Al(iBu) 2H/Al2Et3Cl3 systems exhibited the highest catalytic efficiency, yielding 6-10 polymer chains per Nd atom in the presence of 20 equiv. CTA. Kinetic examination revealed that Nd(OiPr) 3/Al(iBu)2H/Me2SiCl2 and Nd(OiPr)3/Al(iBu)2H/Al2Et3Cl 3 catalytic systems proceeded with fully- and semi-reversible chain transfer reactions, respectively. Quantitative formation of polymers was observed in each step of the 1,3-butadiene seeding polymerization, indicating the living mode of the two catalytic systems. Moreover, the triblock copolymers, PBD-b-PIP-b-PBD and PBD-b-PIP-b-PCL, were successfully synthesized with Nd(OiPr)3/Al(iBu)2H/Me2SiCl2 catalytic system.",

keywords = "1,3-Butadiene, Coordinative chain transfer polymerization, Neodymium-based catalyst",

author = "Feng Wang and Heng Liu and Wenjie Zheng and Jun Guo and Chunyu Zhang and Liping Zhao and Hexin Zhang and Yanming Hu and Chenxi Bai and Xuequan Zhang",

note = "Funding Information: The authors appreciate financial supports from the National Science and Technology Infrastructure Program ( 2007BAE14 B01-06 ), The Fund for National Natural Scientific Foundation of China (No. 20974016 and No. 51203147 ), The Jilin Provincial Research Fund for Basic Research, China (No. 20130102007JC ). ",

year = "2013",

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doi = "10.1016/j.polymer.2013.10.031",

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T1 - Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems

AU - Wang, Feng

AU - Liu, Heng

AU - Zheng, Wenjie

AU - Guo, Jun

AU - Zhang, Chunyu

AU - Zhao, Liping

AU - Zhang, Hexin

AU - Hu, Yanming

AU - Bai, Chenxi

AU - Zhang, Xuequan

N1 - Funding Information: The authors appreciate financial supports from the National Science and Technology Infrastructure Program ( 2007BAE14 B01-06 ), The Fund for National Natural Scientific Foundation of China (No. 20974016 and No. 51203147 ), The Jilin Provincial Research Fund for Basic Research, China (No. 20130102007JC ).

PY - 2013/11/27

Y1 - 2013/11/27

N2 - Coordinative chain transfer polymerization (CCTP) of 1,3-butadiene was assessed by employing several traditional Ziegler-Natta type Nd-based catalytic systems. Both the types of alkylaluminum as CTA and chloride donor as third component significantly affected the chain transfer characteristic of the CCTP systems. Among the catalytic systems examined, Nd(OiPr)3/Al(iBu) 2H/Me2SiCl2 and Nd(OiPr)3/Al(iBu) 2H/Al2Et3Cl3 systems exhibited the highest catalytic efficiency, yielding 6-10 polymer chains per Nd atom in the presence of 20 equiv. CTA. Kinetic examination revealed that Nd(OiPr) 3/Al(iBu)2H/Me2SiCl2 and Nd(OiPr)3/Al(iBu)2H/Al2Et3Cl 3 catalytic systems proceeded with fully- and semi-reversible chain transfer reactions, respectively. Quantitative formation of polymers was observed in each step of the 1,3-butadiene seeding polymerization, indicating the living mode of the two catalytic systems. Moreover, the triblock copolymers, PBD-b-PIP-b-PBD and PBD-b-PIP-b-PCL, were successfully synthesized with Nd(OiPr)3/Al(iBu)2H/Me2SiCl2 catalytic system.

AB - Coordinative chain transfer polymerization (CCTP) of 1,3-butadiene was assessed by employing several traditional Ziegler-Natta type Nd-based catalytic systems. Both the types of alkylaluminum as CTA and chloride donor as third component significantly affected the chain transfer characteristic of the CCTP systems. Among the catalytic systems examined, Nd(OiPr)3/Al(iBu) 2H/Me2SiCl2 and Nd(OiPr)3/Al(iBu) 2H/Al2Et3Cl3 systems exhibited the highest catalytic efficiency, yielding 6-10 polymer chains per Nd atom in the presence of 20 equiv. CTA. Kinetic examination revealed that Nd(OiPr) 3/Al(iBu)2H/Me2SiCl2 and Nd(OiPr)3/Al(iBu)2H/Al2Et3Cl 3 catalytic systems proceeded with fully- and semi-reversible chain transfer reactions, respectively. Quantitative formation of polymers was observed in each step of the 1,3-butadiene seeding polymerization, indicating the living mode of the two catalytic systems. Moreover, the triblock copolymers, PBD-b-PIP-b-PBD and PBD-b-PIP-b-PCL, were successfully synthesized with Nd(OiPr)3/Al(iBu)2H/Me2SiCl2 catalytic system.

KW - 1,3-Butadiene

KW - Coordinative chain transfer polymerization

KW - Neodymium-based catalyst

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VL - 54

SP - 6716

EP - 6724

JO - Polymer

JF - Polymer

IS - 25

ER -

Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems

Abstract

Bibliographical note

Keywords

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