ACYCLIC DIENE METATHESIS POLYMERIZATION OF TAILOR-MADE MONOMERS TOWARDS SEQUENCE-REGULATED VINYL COPOLYMERS

Zi-long Li; Lei Li; Fu-sheng Du; Zi-chen Li

doi:10.1007/s10118-013-1227-6

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ACYCLIC DIENE METATHESIS POLYMERIZATION OF TAILOR-MADE MONOMERS TOWARDS SEQUENCE-REGULATED VINYL COPOLYMERS

NOTE | Updated：2023-01-03

- ACYCLIC DIENE METATHESIS POLYMERIZATION OF TAILOR-MADE MONOMERS TOWARDS SEQUENCE-REGULATED VINYL COPOLYMERS
- Chinese Journal of Polymer Science Vol. 31, Issue 2, Pages: 355-362(2013)
- Affiliations：
  
  Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Polymer Chemistry & Physics of Ministry of Education, Department of Polymer Science & Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
- Author bio：
  
  **Zi-Chen Li (李子臣), E-mail: zcli@pku.edu.cn
- Funds：
- DOI：10.1007/s10118-013-1227-6
  CLC：
- Received：11 September 2012，
  
  Accepted：30 October 2012，
  
  Published：2013-02
- Accepted：
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Zi-long Li, Lei Li, Fu-sheng Du, et al. ACYCLIC DIENE METATHESIS POLYMERIZATION OF TAILOR-MADE MONOMERS TOWARDS SEQUENCE-REGULATED VINYL COPOLYMERS[J]. Chinese Journal of Polymer Science, 2013, 31(2): 355-362.
DOI：

Zi-long Li, Lei Li, Fu-sheng Du, et al. ACYCLIC DIENE METATHESIS POLYMERIZATION OF TAILOR-MADE MONOMERS TOWARDS SEQUENCE-REGULATED VINYL COPOLYMERS[J]. Chinese Journal of Polymer Science, 2013, 31(2): 355-362. DOI： 10.1007/s10118-013-1227-6.

摘要

Abstract

Acyclic diene metathesis polymerization (ADMET) enables convenient transfer of sequential information of the designed monomers to the corresponding sequence-regulated copolymers. In this study

two structurally symmetric monomers

M1 and M2

were synthesized

via

atom transfer radical addition (ATRA) of diethyl

meso

-2

5-dibromohexanedioate with 1

5-hexadiene and 1

7-octadiene

respectively. Thus

sequenced segment of VB-EA-EA-VB (VB and EA represent vinyl bromide and ethyl acrylate

respectively) was incorporated into the ADMET diene monomers. ADMET polymerization of these two monomers with Grubbs first generation catalyst (Grubbs-I) was performed in CH

at 40℃ for 5 days under nitrogen purge. Effects of catalyst amount

monomer concentration and methanol precipitation on the

and PDI of polymers were investigated by GPC

and the structures of the formed polymers were characterized by NMR. Our results indicate that using 3.0 mol% of Grubbs-I to monomer can afford polymers with high

. Moreover

selective precipitation in methanol enables complete removal of low molecular weight components from the crude products. Meanwhile

M2 exhibits higher ADMET polymerization reactivity than M1 due to its capability of suppressing negative neighboring group effect.

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