Rapid and Scalable Access to Sequence‐Controlled DHDM Multiblock Copolymers by FLP Polymerization

Abstract

An immortal N‐(diphenylphosphanyl)‐1,3‐diisopropyl‐4,5‐dimethyl‐1,3‐dihydro‐2H‐imidazol‐2‐imine/diisobutyl (2,6‐di‐tert‐butyl‐4‐methylphenoxy) aluminum (P(NIiPr)Ph2/(BHT)AliBu2)‐based frustrated Lewis pair (FLP) polymerization strategy is presented for rapid and scalable synthesis of the sequence‐controlled multiblock copolymers at room temperature. Without addition of extra initiator or catalyst and complex synthetic procedure, this method enabled a tripentacontablock copolymer (n=53, k=4, dpn=50) to be achieved with the highest reported block number (n=53) and molecular weight (Mn=310 kg mol−1) within 30 min. More importantly, this FLP polymerization strategy provided access to the multiblock copolymers with tailored properties by precisely adjusting the monomer sequence and block numbers.

Use of anN-heterocyclic carbene (NHC)-based interacting Lewis pair for the synthesis of a cyclic poly(alkyl acrylate)viachain-growth polymerization and subsequent ring-closing without extreme dilution

“…19 Furthermore, Zhang et al discovered that LPP using FLP showed a high degree of living polymerization character and succeeded in synthesizing multi-block copolymers. 20 In addition, the polymerization of alkyl sorbate was performed using several LPs, and then the conditions of LPP were optimized and the topology was induced to the cyclic structure. 21,22 In general, Lewis pairs are categorized into (1) classical Lewis adduct (CLA), (2) FLP, and (3) interacting Lewis pair (ILP) (Fig.…”

“…[19][20][21][22][23][24][25][26][27][28][29][30][31][32] The CLA is inactive for many reactions and recent progress focused on FLP showed that it is remarkable, i.e., an NHC with a bulky substituent combined with Al (C 6 F 5 ) 3 does not form the corresponding CLA complex, and, therefore, shows catalytic activation for some polymerizations of vinyl monomers. [19][20][21][22][23][24][25][26][27][28][29][30][31][32] On the other hand, the ILPs are more stable and show a different spectrum pattern from the original substances, and may possibly exhibit chemoselectivity, but there are a few reports concerned with such kinds of viewpoints. This research background prompted us to investigate which type of Lewis pair should NHCtBu/MAD be categorized.…”