Triblock and pentablock terpolymers by sequential base-assisted living cationic copolymerization of functionalized vinyl ethers

Abstract

A series of novel, well-defined triblock and pentablock terpolymers of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiEGVE) were synthesized by sequential base-assisted living cationic polymerization.

Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers

“…This case is referred as a nonideal non-azeotropic copolymerization [42]. Found in the literature, conventional cationic polymerization has been employed for the synthesis of statistical copolymers containing CEVE monomer units and block copolymers with PCEVE polymer chains [43,44,45,46]. There are very few detailed studies leading to the calculation of the reactivity ratios, however.…”

A well-defined block copolymer synthesis via living cationic polymerization and nitroxide-mediated polymerization using carboxylic acid-based alkoxyamines as a dual initiator

“…The precipitation was no longer observed, but the polymerization did not occur under the truly living/controlled conditions as indicated by the broad dispersity (1.9) and low chain-end functionality (40%, entry 5, Table 1). The non-living/controlled polymerization of a protonic acid/Lewis acid system in a polar solvent 7 as well as benzoic acid/zinc chloride initiating systems 9 was also reported. The reason could be that the propagation rate was much faster than the initiation, which led to a low initiator efficiency.…”

“…5 Following the discovery of a hydrogen iodide/iodine initiating system by Higashimura and Sawamoto, 6 a variety of binary initiating systems consisting of protonic acid/Lewis acid were developed to polymerize vinyl ether monomers in a living/controlled manner. [7][8][9][10][11][12][13] Hence, various functional block copolymers composed of vinyl ether monomer units were synthesized acting as polymer surfactants, 14,15 antibacterial agents, [16][17][18][19][20][21] glycopolymer stimuli-responsive micelles and gels, 16,[18][19][20][21] thermoplastic elastomers, 22,23 or optical plastics. 24 By combination those binary initiating systems with living/ controlled radical polymerization techniques such as reversible addition-fragmentation transfer polymerization (RAFT) or atom transfer radical polymerization (ATRP), block-, statisticaland graft copolymers of vinyl ether monomers with radically polymerizable monomers have been subsequently achieved using the chain-end chemical transformation strategy or the use of a dual initiator.…”

Recent advances in applications of vinyl ether monomers for precise synthesis of custom-tailored polymers

“…For example, ABAtriblock copolymers of adamantyl vinyl ether with NBVE were produced by cationic polymerization with a difunctional initiating system 1,4-bis(1-acetoxy)butane/Et 1,5 AlCl 1,5 /ethyl acetate [180], while introducing cyclohexanedimethanol divinyl ether to this system afforded star-diblock copolymers featuring improved rubber elastic properties. A similar sequential protocol afforded tri-and pentablock copolymers of NBVE, CEVE and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiEGVE) [181]. Diblock copolymers of IBVE and -methylstyrene were also produced by sequential approach with initiation by HBr/FeCl 3 /nBu 4 NBr [182].…”