Construction of Sequence-Regulated Vinyl Copolymers via Iterative Single Vinyl Monomer Additions and Subsequent Metal-Catalyzed Step-Growth Radical Polymerization

Abstract

A series of sequence-regulated vinyl copolymers with high-order and long vinyl monomer sequences were constructed via a combination of iterative single vinyl monomer additions, which were mediated by radical and cationic intermediates, and subsequent metal-catalyzed step-growth radical polymerization. The construction of vinyl monomer sequences was attained by iterative single monomer radical and cationic additions between a dichloride, having a similar substituent to that of vinyl monomers, and vinyl monomers such as styrenes, acrylates, and acrylonitrile. The resulting products were converted into sequenceregulated ab-type monomers that have embedded vinyl monomer sequences between an unconjugated CC bond and reactive C−Cl bond via selective allylation of one of the two C−Cl bonds at their terminals. The synthesized sequence-regulated ab-type monomers were polymerized via metal-catalyzed stepgrowth radical polymerization, which resulted in vinyl chloride units via repetitive intermolecular addition reactions between the CC and C−Cl terminals. Alternatively, aa-and bb-type sequence-regulated monomers, which have two unconjugated CC and two reactive C−Cl bonds, respectively, were prepared by similar iterative single monomer additions and were subsequently polymerized via metalcatalyzed step-growth radical polymerization. The repeating vinyl monomer sequence codes in the resulting polymers, such as ABCC, ABCD, ABBAC, ABDBAC, and ABDBACAEEAC, varied from 4 to 11 monomer units in which the embedded vinyl monomer units were styrenes, acrylates, acrylamides, acrylonitrile, vinyl chloride, vinylidene chloride, and ethylene.

Unzipping and scrambling reaction‐induced sequence control of copolymer chains via temperature changes during cationic ring‐opening copolymerization of cyclic acetals and cyclic esters

“…NMR spectra were recorded using a JEOL JNM-ECA 500 instrument (500. 16 MHz for 1 H and 125.77 MHz for 13 C) or a JEOL JNM-ECS 400 instrument (100.53 MHz for 13 C). Electrospray ionization mass spectrometry (ESI-MS) was performed on an LTQ Orbitrap XL (Thermo Scientific).…”

“…Sequenceregulated copolymers have been synthesized via several methods. [12][13][14][15][16][17][18][19][20][21][22][23][24] Each method has inherent advantages and disadvantages. For example, step-by-step monomer addition to a polymer chain (iterative method) 12,13 is the most promising strategy for producing desired sequences, although a considerable amount of time and effort is necessary to generate a long chain.…”

“…Polymerization of a monomer containing specific sequences of multiple monomer units is also very effective; however, the synthesis of such sequence-incorporated monomers usually requires cumbersome procedures. [14][15][16][17] Polymerization of monomers with specific reactivities is the most practical method, although the need for very high selectivity during the propagation reactions limits the monomers that can be used. [4][5][6][7][8][9][10][11]18,19 A new strategy and/or hybridization of existing methods are required for the synthesis of a much wider variety of sequence-regulated copolymers in a practical manner.…”

Periodically Functionalized Sequence‐Regulated Vinyl Polymers via Iterative Atom Transfer Radical Additions and Acyclic Diene Metathesis Polymerization

“…Among them, iterative single monomer insertion (SUMI) or addition based on atom transfer radical addition (ATRA) and reversible addition‐fragmentation chain transfer (RAFT) reaction is effective for step‐by‐step connection of vinyl monomers to construct perfectly sequence‐defined oligomers; however, there are limitations in the number of monomer units due to decreased yields and difficulty in isolating the products along with the cumulative processes and molecular weights. [ 21–49 ]…”

2,5‐Dimethylfuran/Acrylonitrile as Latent Monomer for Sequence‐Controlled Copolymer and Sequence‐Dependent Thermo‐Responsivity

“…Despite the great challenge, the sequence control in radical polymerization has gained enormous progress in past decades. [ 23,24 ] For example, Sawamoto et al. developed concurrent tandem catalysis‐based methodology, [ 25–28 ] template‐initiator, [ 29,30 ] template‐monomer strategies [ 14,15,31–34 ] for generating the sequence‐controlled polymers.…”