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Hyperbranched Aliphatic Polyester via Cross‐Metathesis Polymerization: Synthesis and Postpolymerization Modification
Author(s) -
Zeng FuRong,
Ma JiMei,
Sun LinHao,
Zeng Zhen,
Jiang Hong,
Li ZiLong
Publication year - 2018
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201700658
Subject(s) - polymer chemistry , differential scanning calorimetry , polyester , gel permeation chromatography , polymerization , acrylate , surface modification , monomer , thermal stability , chemistry , polymer , materials science , methyl acrylate , glass transition , organic chemistry , physics , thermodynamics
A novel postpolymerization modification methodology is demonstrated to achieve selective functionalization of hyperbranched polymer (HBP). Terminal and internal acrylates of HBP derived from cross‐metathesis polymerization (CMP) are functionalized in a chemoselective fashion using the thiol‐Michael chemistries. Model reactions between different thiols (benzyl mercaptan and methyl thioglycolate) and acrylates ( n ‐hexyl acrylate and ethyl trans ‐2‐decenoate) by using dimethylphenylphosphine or amylamine as the catalyst are investigated to optimize the modification protocol for HBP. High‐molecular‐weight HBP P0 is generated through CMP of AB 2 monomer 2 , a compound containing one α‐olefin and two acrylate metathetically polymerizable groups. CMP kinetics is monitored by NMR and gel permeation chromatography (GPC). Accordingly, microstructural analysis is conducted in detail, and CMP procedure is optimized. Postpolymerization modification of HBP P0 is performed via two distinguished strategies, namely one‐step complete modification and sequential modification, to generate terminally and/or internally functionalized HBPs P1 – P3 in a chemoselective fashion by using phosphine‐initiated and/or base‐catalyzed thiol‐Michael chemistries. Finally, thermal stability and glass transition behaviors of HBPs P0 – P3 are studied by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively.