Kotaro Satoh 교수

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTStereospecific Living Radical Polymerization: Dual Control of Chain Length and Tacticity for Precision Polymer SynthesisKotaro Satoh and Masami KamigaitoView Author Information Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan To whom correspondence should be addressed. E-mail: [email protected]. Phone: +81-52-789-5400. Fax: +81-52-789-5112.Cite this: Chem. Rev. 2009, 109, 11, 5120–5156Publication

Sequence control in chain-growth polymerization is still one of the most challenging topics in synthetic polymer chemistry in contrast to natural macromolecules with completely sequence-regulated structures like proteins and DNA. Here, we report the quantitative and highly selective 1:2 sequence-regulated radical copolymerization of naturally occurring (+)-d-limonene (L) and a maleimide (M) in fluoroalcohol giving chiral copolymers with high glass transition temperatures (220-250 degrees C) orig

This study shows that ytterbium triflate [Yb(OTf)3; OTf = OSO2CF3] induces cationic polymerizations of isobutyl vinyl ether (IBVE) and p-methoxystyrene (pMOS) in aqueous media in conjunction with the hydrogen chloride−vinyl monomer adduct [CH3−CHR−Cl; R = OiBu, C6H4−OCH3] as the initiator at room temperature. These “suspension” polymerizations are carried out by adding neat monomer and then a solution of the initiator into an aqueous solution of Yb(OTf)3 under vigorous stirring, and the polymeri

End-functionalized polyethylene oxides containing cleavable acetal and clickable azide terminal groups (PEO-acetal-N3 and N3-acetal-PEO-acetal-N3) were obtained by the reaction between commercially available PEOs and 2-chloroethyl vinyl ether using pyridinium p-toluenesulfonate. This results in acetal-linkages which can be further functionalized by nucleophilic displacement with sodium azide. Both reactions proceeded quantitatively to produce clickable and cleavable PEOs in good yields. The obta

The most abundant naturally occurring terpene, α-pinene, which cannot be directly polymerized into high polymers by any polymerization method, was quantitatively converted under visible-light irradiation into pinocarvone, which possesses a reactive exo methylene group. The bicyclic vinyl ketone was quantitatively polymerized in fluoroalcohols by selective (99%) ring-opening radical polymerization of the four-membered ring, which results in unique polymers containing chiral six-membered rings wit

A controlled cationic polymerization of styrene was achieved with an alcohol [water−vinyl monomer adduct: CH3CR(Ph)OH; −R = −H (2), −CH3 (3)] as an initiator coupled with BF3OEt2. In the presence of a fairly large amount of water, the polymerization gave polymers with molecular weights that increased in direct proportion to monomer conversion and agreed well with the calculated values, assuming that one initiator molecule generates one polymer chain, although the molecular weight distributions (

From naturally occurring β-methylstyrenes, such as anethole and isoeugenol, a bio-based copolymer was prepared by the controlled cationic copolymerization with the alcohol/BF3OEt2 initiating system in an aqueous solvent. The copolymerizations with p-methoxystyrene proceeded in a living fashion, in which the molecular weights and molecular weight distributions of the resulting copolymers were controlled. Specifically, isoeugenol can be copolymerized without protection of the phenolic moiety to gi

Emulsion cationic polymerization in water was achieved with rare earth metal triflates [Ln(OTf)3; Ln = Yb, Sc, Dy, Sm, Gd, and Nd; OTf = OSO2CF3] that are well-known as water-tolerant Lewis acids. Even in the presence of a large amount of surfactants such as dodecylammonium halides, sodium laurylbenzenesulfate, and poly(vinyl methyl ether), Ln(OTf)3 induced cationic polymerizations of p-methoxystyrene (pMOS) in aqueous media in conjunction with the pMOS−HCl adduct (1) at 30 °C. In particular, th

One-shot control of comonomer sequence distributions was demonstrated by dual radical and cationic copolymerization using RAFT mediator.

A new class of polymerizations was developed via metal-catalyzed C-C bond forming radical polyaddition; the monomers were designed to have a reactive C-Cl bond, which can be activated by the metal catalysts to generate a carbon radical species, along with a C=C double bond, to which the carbon radical generated from another molecule adds to form a C-C backbone polymer with an inactive C-Cl pendant.

Naturally abundant caffeic acid, a cinnamic acid derivative with a catechol group in its structure, was quantitatively converted into a series of protected vinyl catechol (VC) derivatives via facile and scalable decarboxylation and protection reactions. Controlled radical polymerizations of the protected VCs proceeded well using the appropriate reversible addition–fragmentation chain transfer agent or alkoxyamine to generate well-defined polymers, although the reaction rates and molecular weight

This study shows that BF3OEt2 induces living cationic polymerization of p-alkoxystyrenes and their living copolymerization with p-hydroxystyrene (pHS) without protection of the phenolic group. Similar to pHS, controlled cationic polymerizations of p-methoxystyrene (pMOS) and p-tert-butoxystyrene (tBOS) were achieved by combination of the water adduct of pMOS [1; CH3CH(C6H4-p-OCH3)OH] and BF3OEt2 in the presence of a fairly large amount of water (equimolar to the monomer or 100 molar excess over

Direct living cationic polymerization of p-hydroxystyrene (pHS) has been developed in the presence of a fairly large amount of water using BF3OEt2 as a Lewis acid catalyst and the adducts (1−4) of p-methoxystyrene (pMOS) and a series of protonic compounds as initiators. In contrast to most living cationic polymerizations, the water and the alcohol adducts (3 and 4, respectively) produced polymers with number-average molecular weights (Mn) close to the calculated values from the monomer/initiator