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.

Monomer sequence control in terms of a single monomer unit, particularly in vinyl polymers, is one of the largest challenges in polymer chemistry. Furthermore, multifactor control of monomer sequence, molecular weight, and stereoregularity is an ultimate goal. In this work, we propose a strategy to prepare C–C main-chain sequence-regulated polymers with controlled molecular weights from vinyl monomers via a combination of iterative atom transfer radical additions and olefin metathesis reactions. This strategy enabled the synthesis of sequence-regulated polymers with exact styrene–acrylate–styrene sequences in the C–C main chains, controlled molecular weights of up to 104, and stereoregularities varying with syndiotacticity, isotacticity, and heterotacticity. The utility of this strategy is further demonstrated by formation of block copolymers consisting of sequence-regulated vinyl polymer segments by combining living ROMP of norbornene derivatives.

An epoxy derivative of a naturally occuring vinylphenolic compound, 4-vinylguaiacol (4VGEP), was used for the synthesis of a well-defined (Mw/Mn = 1.08-1.14), bio-based styrene-type polymer. Block copolymers of 4VGEP with...

Iterative ATRAs and ADMET polymerization enabled the synthesis of sequence-regulated vinyl polymers without statistical distribution of monomer compositions and sequences.