Highly <italic style="font-style: italic">Cis</italic>-1,4 Selective Polymerization of Conjugated Dienes Catalyzed by <italic style="font-style: italic">N</italic>-heterocyclic Carbene-ligated Neodymium Complexes

Shu Zhang; Na Wu; Yi-Xian Wu

doi:10.1007/s10118-020-2460-4

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Highly Cis-1,4 Selective Polymerization of Conjugated Dienes Catalyzed by N-heterocyclic Carbene-ligated Neodymium Complexes

ARTICLE | Updated：2020-07-27

- Highly Cis-1,4 Selective Polymerization of Conjugated Dienes Catalyzed by N-heterocyclic Carbene-ligated Neodymium Complexes
- Chinese Journal of Polymer Science Vol. 38, Issue 12, Pages: 1305-1312(2020)
- Affiliations：
  
  State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
- Author bio：
  
  wuyx@mail.buct.edu.cn
- Funds：
- DOI：10.1007/s10118-020-2460-4
  CLC：
- Received：01 April 2020，
  
  Revised：2020-5-19，
  
  Accepted：20 May 2020，
  
  Online First：27 July 2020，
  
  Published：10 September 2020
- Accepted：
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Zhang, S.; Wu, N.; Wu, Y. X. Highly , cis,-1,4 selective polymerization of conjugated dienes catalyzed by , N,-heterocyclic carbene-ligated neodymium complexes. Chinese J. Polym. Sci. 2020, 38, 1305–1312

Shu Zhang, Na Wu, Yi-Xian Wu. Highly Cis-1,4 Selective Polymerization of Conjugated Dienes Catalyzed by N-heterocyclic Carbene-ligated Neodymium Complexes[J]. Chinese Journal of Polymer Science, 2020, 38(12): 1305-1312. DOI: 10.1007/s10118-020-2460-4.
Zhang, S.; Wu, N.; Wu, Y. X. Highly , cis,-1,4 selective polymerization of conjugated dienes catalyzed by , N,-heterocyclic carbene-ligated neodymium complexes. Chinese J. Polym. Sci. 2020, 38, 1305–1312 DOI： 10.1007/s10118-020-2460-4.

Shu Zhang, Na Wu, Yi-Xian Wu. Highly Cis-1,4 Selective Polymerization of Conjugated Dienes Catalyzed by N-heterocyclic Carbene-ligated Neodymium Complexes[J]. Chinese Journal of Polymer Science, 2020, 38(12): 1305-1312. DOI: 10.1007/s10118-020-2460-4. DOI：

摘要

Abstract

Neodymium complexes containing

-heterocyclic carbene (NHC) ligands

NdCl

3-R

(NCH=)

C:]·THF

(

Nd1

: R = 2

= 0;

Nd2

: R = 2

6-Et

= 1;

Nd3

: R = 2

6-Me

= 1) were synthesized and employed as precatalysts for the coordination polymerization of conjugated dienes (butadiene and isoprene). In combination with triisobutylaluminium (TIBA)

Nd1

promoted butadiene polymerization to produce extremely high

cis

-1

4 (up to 99.0%) polybutadienes with high molecular weight (

= 250−780 kg·mol

−1

). The

Nd1

/TIBA catalytic system also exhibited both high catalytic activity and

cis

-1

4 selectivity (up to 97.8%) for isoprene polymerization. The catalytic activity

molecular weight and molecular weight distribution of resulting polydienes were directly influenced by Al/Nd molar ratio

aging method

and polymerization temperature. Very interestingly

the high

cis

-1

4 selectivity of the catalyst towards butadiene and isoprene kept almost unchanged under different reaction conditions. The

cis

-1

4 polyisoprenes with high molecular weight (

= 210−530 kg·mol

−1

) and narrow molecular weight distribution (

= 1.9−2.7) as well as high

cis

-1

4 selectivity (~97%) could be synthesized by using the aged

Nd1

/TIBA catalytic system in the presence of isoprene (100 equivalent to Nd) at low Al/Nd molar ratios of 6−10. Polyisoprenes with low molecular weights (

= 12−76 kg·mol

−1

) and narrow molecular weight distributions (

= 1.7−2.6) were obtained by using

Nd2

and

Nd3

as precatalysts

indicating that the molecular weight of resulting polyisoprenes can be adjusted by changing the substitutes of ligand in Nd complex.

关键词

Keywords

references

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⁰

Highly Cis-1,4 Selective Polymerization of Conjugated Dienes Catalyzed by N-heterocyclic Carbene-ligated Neodymium Complexes

DOI：10.1007/s10118-020-2460-4

摘要

Abstract

关键词

Keywords

references