Living, isoselective polymerization of 4-methyl-1,3-pentadiene and styrenic monomers and synthesis of highly stereoregular block copolymers via sequential monomer addition

TitleLiving, isoselective polymerization of 4-methyl-1,3-pentadiene and styrenic monomers and synthesis of highly stereoregular block copolymers via sequential monomer addition
Publication TypeArticolo su Rivista peer-reviewed
Year of Publication2011
AuthorsCapacchione, C., Saviello D., Ricciardi Rosa, and Proto A.
JournalMacromolecules
Volume44
Pagination7940-7947
ISSN00249297
Keywords1, 3-butadiene, Block copolymers, Butadiene, Copolymer blocks, Copolymerization, Isoselective polymerization, Isotactic polymers, Isotactics, Living polymerization, Low molecular weight, Methylaluminoxane, Monomer addition, Monomers, Polymer chains, Polymerization mechanisms, Polymers, Polystyrenes, Room temperature, Stereoregular, Styrenic monomers, Thermal features, Titanium, Titanium complexes, Titanium compounds
Abstract

The living, isoselective polymerization of 4-methyl-1,3-pentadiene, 4-methylstyrene, and 4-tert-butylstyrene was promoted by using the titanium complex 1 activated by methylaluminoxane (MAO) at room temperature producing highly isotactic polymers. The synthesis of highly isotactic polystyrene-block-poly(4-methyl-1,3-pentadiene), poly(4-methylstyrene)-block- polystyrene, poly(4-methylstyrene)-block-1,4-trans-poly(1,3-butadiene), poly(4-methylstyrene)-block-polystyrene-block-poly(4-methylstyrene), poly(4-methylstyrene)-block-polystyrene-block-poly(4-methyl-1,3-pentadiene), and poly(4-methylstyrene)-block-polystyrene-block-poly(4-tert-butylstyrene) copolymers was also accomplished for the first time, by sequential monomer addition, in the presence of the system 1 activated by MAO. The thermal features of these polymers clearly show that all copolymer blocks, except the 4-methylstyrene one, are crystalline with melting point values typical of the corresponding homopolymers. The synthesis of a low molecular weight polystyrene sample allowed us to detect the polymer chain ends, giving useful information about the polymerization mechanism. © 2011 American Chemical Society.

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URLhttps://www.scopus.com/inward/record.uri?eid=2-s2.0-80054970824&doi=10.1021%2fma201442w&partnerID=40&md5=d2cbc7073b7ad0eef53fce9f1ea400d2
DOI10.1021/ma201442w