Highly cis‐1, 4 Selective Living Polymerization of Unmasked Polar 2‐(2‐Methylidenebut‐3‐enyl)Furan and Diels–Alder Addition. Issue 17 (27th July 2017)

• Record Type: Journal Article
• Authors: Long, Shiyu; Lin, Fei; Yao, Changguang; Cui, Dongmei
• Is Part Of: Macromolecular rapid communications. Volume 38:Issue 17(2017)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2017-07-27
• Subjects: elastomers -- living polymerization -- metal–organic catalysts -- microstructure -- polar monomers; Macromolecules -- Periodicals; Polymers -- Periodicals; Chemistry -- Periodicals; 547.705
• DOI: 10.1002/marc.201700227
• Languages: English
• ISSNs: 1022-1336

Abstract

Abstract : A novel polar polydiene with high cis ‐1, 4 selectivity (98.6%) and narrow polydispersity ( M w / M n = 1.17) is achieved through the coordination living polymerization of a new polar diene‐based monomer. Moreover, a variety of functional rubber materials can be obtained via mild Diels–Alder addition with furan groups on the side chain of the polymer. Abstract : The polymerization of a new polar diene‐based monomer 2‐(2‐methylidenebut‐3‐enyl)furan (MBEF) without masking is achieved by using the bis(phosphino)carbazoleide‐ligated yttrium (Y) alkyl complex upon the activation of [Ph3 C][B(C6 F5 )4 ]. Under mild conditions, the polymerizations under the monomer‐to‐Y ratios ranging from 100:1 to 500:1 perform fluently in high yields. The afforded polydienes bearing pendant terminal furan groups have high cis ‐1, 4‐regularity up to 98.6% and molecular weights close to the theoretic values and narrow polymer dispersity index(PDI) (1.13–1.17) suggesting a livingness polymerization mode. In addition, this novel polydiene is an excellent building block for preparing functional rubber materials. For example, via Diels–Alder addition of furan groups under mild conditions, hydroxyl groups are successfully introduced on the side chains efficiently in a 75% conversion. Furthermore, the copolymerization of polar MBEF and nonpolar isoprene is also successfully realized by the bis(phosphino) carbazoleide‐ligated scandium analog to access furan‐modified cis ‐1, 4 (>97%) polyisoprene with different MBEF contents (5.3%, 8.7%).