期刊
POLYMER CHEMISTRY
卷 12, 期 34, 页码 4974-4985出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1py00971k
关键词
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资金
- National Natural Science Foundation of China [U1463201, 21522604]
- National Key Research and Development Program of China [2017YFC1104802]
- Natural Science Foundation of Jiangsu Province, China [BK20150031]
- Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM)
- Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
- Top-Notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP)
An innovative strategy using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent was proposed to copolymerize four distinct types of monomers (ABCD) in one pot, achieving the synthesis of tetrablock quaterpolymers. By sequentially feeding monomers and utilizing dual-switch mechanisms, the study successfully combined cRAFT, rRAFT, and ROPs for the rational design and precise synthesis of multiblock copolymers with advanced architectures and functionalities.
Olefin monomers are divided into cationically polymerizable ones (monomer A, such as vinyl ethers) and radically polymerizable ones (monomer B, such as acrylates); in parallel, cyclic ester monomers are polymerizable either electrophilically (monomer C, such as lactones) or nucleophilically (monomer D, such as lactides). To address the challenge of polymerizing the distinctive four types of monomers in one pot into ABCD type tetrablock copolymers, we proposed a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent bearing both the RAFT polymerization site and ring-opening polymerization (ROP) site. The RAFT site was able to copolymerize A and B via switching the cationic RAFT polymerization (cRAFT) to radical RAFT polymerization (rRAFT). Subsequently, the ROP site copolymerized C and D by switching the electrophilic ROP to nucleophilic ROP. A general dual-switch strategy of both RAFT and ROP mechanism transitions successfully produced ABCD-type tetrablock quaterpolymers in one pot by sequential monomer feeding. Poly(isobutyl vinyl ether)-b-poly(methyl methacrylate)-b-poly(delta-valerolactone)-b-polylactide (PIBVE-b-PMMA-b-PVL-b-PLA) was synthesized. All synthesized homopolymers and multi-block copolymers exhibited predicted molecular weights and relatively narrow dispersities (D <= 1.45). The copolymerization strategy paved a new avenue to combine cRAFT, rRAFT and ROPs to copolymerize vinyl and cyclic ester monomers for rational design and precise synthesis of multiblock copolymers with advanced architectures and functionalities.
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