Ethylene Polymerization and Copolymerization with Polar Monomers by Benzothiophene-bridged BPMO-Pd Catalysts

Hong-Liang Mu; Jun-Hao Ye; Guang-Lin Zhou; Kang-Kang Li; Zhong-Bao Jian

doi:10.1007/s10118-020-2359-0

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Ethylene Polymerization and Copolymerization with Polar Monomers by Benzothiophene-bridged BPMO-Pd Catalysts

ARTICLE | Updated：2019-11-27

- Ethylene Polymerization and Copolymerization with Polar Monomers by Benzothiophene-bridged BPMO-Pd Catalysts
- Chinese Journal of Polymer Science Vol. 38, Issue 6, Pages: 579-586(2020)
- Affiliations：
  
  State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
- Author bio：
  
  zbjian@ciac.ac.cn
- Funds：
- DOI：10.1007/s10118-020-2359-0
  CLC：
- Received：26 August 2019，
  
  Revised：2019-9-19，
  
  Accepted：23 September 2019，
  
  Online First：27 November 2019，
  
  Published：2020-06
- Accepted：
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Mu, H. L.; Ye, J. H.; Zhou, G. L.; Li, K. K.; Jian, Z. B. Ethylene polymerization and copolymerization with polar monomers by benzothiophene-bridged BPMO-Pd catalysts. Chinese J. Polym. Sci. 2020, 38, 579–586

Hong-Liang Mu, Jun-Hao Ye, Guang-Lin Zhou, et al. Ethylene Polymerization and Copolymerization with Polar Monomers by Benzothiophene-bridged BPMO-Pd Catalysts[J]. Chinese Journal of Polymer Science, 2020, 38(6): 579-586.
Mu, H. L.; Ye, J. H.; Zhou, G. L.; Li, K. K.; Jian, Z. B. Ethylene polymerization and copolymerization with polar monomers by benzothiophene-bridged BPMO-Pd catalysts. Chinese J. Polym. Sci. 2020, 38, 579–586 DOI： 10.1007/s10118-020-2359-0.

Hong-Liang Mu, Jun-Hao Ye, Guang-Lin Zhou, et al. Ethylene Polymerization and Copolymerization with Polar Monomers by Benzothiophene-bridged BPMO-Pd Catalysts[J]. Chinese Journal of Polymer Science, 2020, 38(6): 579-586. DOI： 10.1007/s10118-020-2359-0.

摘要

Abstract

A series of new bisphosphine-monoxide (BPMO) ligands based on benzothiophene backbone and the corresponding palladium complexes {к

-2-P(O)(Ph)

-3-PR

-C

S}PdMeCl {

: R

= R

= Ph;

: R

= R

= 2-OMe-Ph;

: R

= R

= 2-CF

-Ph;

: R

= Ph

= 2-(2′

6′-(OMe)

)-C

} were synthesized and fully characterized by

H-

C-

P-

and 2D-NMR spectroscopy and single-crystal X-ray diffraction. In the presence of Na

B[3

5-(CF

)

]

–

(NaBArF)

these complexes showed very high activities (up to 2.0 × 10

g·mol

–1

·h

–1

) for ethylene polymerization. More significantly

these catalysts enabled the copolymerization of ethylene with a broad scope of commercially available polar comonomers such as acrylates

acrylic acid

acrylonitrile

vinyltrialkoxysilane

allyl acetate

and long-chain 6-chloro-1-hexene to give functionalized polyethylene with reasonable catalytic activities (up to 10

g·mol

–1

·h

–1

) and incorporations (up to 5.3 mol%). This contribution suggests that

besides the modulation of conventionally steric and electronic factors

the connectivity (at different linking positions) of BPMO (P

O) donors to the heteroaryl backbone also greatly influences the catalyst properties in terms of catalytic activity

polymer branching content

comonomer scope

and comonomer incorporation.

关键词

Keywords

references

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