Atom transfer radical polymerization.

New polymer synthesis by nitroxide mediated living radical polymerizations.

Metal-catalyzed living radical polymerization.

Controlled/living radical polymerization: Features, developments, and perspectives

Current status and future perspectives in atom transfer radical polymerization (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP. New hybrid materials based on organic/inorganic systems and natural/synthetic polymers are presented. Some current and forthcoming applications are described.

Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives

Iron(II) bis(triphenylphosphine)dichloride [FeCl2(PPh3)2] induced living radical polymerization of methyl methacrylate (MMA) in conjunction with organic halides as initiators [R−X:  CCl4, CHCl2COPh, (CH3)2CBrCO2C2H5, and CH3CBr(CO2C2H5)2] in the absence or presence of Al(OiPr)3 in toluene at 80 °C. The added aluminum compounds were not needed for the Fe(II)-mediated living polymerization unlike the RuCl2(PPh3)3-based counterpart. With CH3CBr(CO2C2H5)2 as initiator, the number-average molecular weights of polymers increased in direct proportion to monomer conversion, and the MWDs were narrow throughout the reactions (Mw/Mn = 1.1−1.3). The polymers possessed one initiator moiety at the α-end per one polymer chain. The tacticity was similar to that prepared by AIBN. These results indicate that the Fe(II) complex is effective in the homolytic and reversible cleavage of the carbon−halogen terminal originating from the halide initiators into a transient radical growing species to induce living MMA polymerization.

Iron(II) Chloride Complex for Living Radical Polymerization of Methyl Methacrylate1

Living Radical Polymerization of Methyl Methacrylate with Ruthenium Complex: Formation of Polymers with Controlled Molecular Weights and Very Narrow Distributions1

Possibility of living radical polymerization of vinyl acetate catalyzed by iron(I) complex

The "cation pool" of an N-acyliminium ion was found to serve as an effective initiator of cationic polymerization of vinyl ethers in a microsystem consisting of two micromixers and a microtube reactor. The polymerization led to very narrow molecular weight distribution (Mw/Mn = 1.14). The molecular weight (Mn) increased linearly with an increase in the amount of the monomer. The carbocationic polymer end was effectively trapped by allyltrimethylsilane. The present observations illustrate the potential of microsystems, in conjunction with the cation pool, to effect polymerization in a highly controlled manner without the deceleration inherent in the dynamic equilibrium between active and dormant species.

Tsuyoshi Ando

Papers

Metal-catalyzed living radical polymerization.

Iron(II) Chloride Complex for Living Radical Polymerization of Methyl Methacrylate1

Living Radical Polymerization of Methyl Methacrylate with Ruthenium Complex: Formation of Polymers with Controlled Molecular Weights and Very Narrow Distributions1

Possibility of living radical polymerization of vinyl acetate catalyzed by iron(I) complex

Cation Pool-Initiated Controlled/Living Polymerization Using Microsystems