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The porphyrin handbook - Kadish K.M.

Kadish K.M. The porphyrin handbook - Academic press, 2000. - 368 p.
Download (direct link): kadishsmishgulilard2000.djvu
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Metalloporphyrins as Catalysts for Precision Macromolecular Synthesis
42
TAKUZO AIDA3 and SHOHEI INOUEb
li Department of Chemistry and Biotechnology, Graduate School of
Engineering,
The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 11 3-8656, japan b
Department of Industrial Chemistry, Faculty of Engineering, Science
University of Tokyo, Kagurazaka, Shinjuku-ku, Tokyo 162-0825, Japan
I.
Introduction.............................................................
.............................................. 133
II. Metalloporphyrins Containing Nontransition
Metals...................................................................
1 34
A. Ring-Opening Polymerization of Heterocyclic
Monomers................................................................
1 34
B. Addition Polymerization of Unsaturated
Monomers.................................................................
.... 145
C. Structure-Reactivity
Relationships............................................................
...................... 146
D. Effect of Axial
Coordination.............................................................
........................... 146
E. Utilization of Steric Hindrance for Acceleration of
Polymerization.................................................. 147
F. Ligand-Exchange Activity (Immortal
Polymerization)..........................................................
........ 149
G. Stereochemical Aspects
.........................................................................
.................... 1 52
III. Metalloporphyrins Containing Transition
Metals...................................................................
... 153
A. Ring-Opening Polymerization of Heterocyclic Monomers
............................................................... 153
B. Addition Polymerization of Unsaturated
Monomers.................................................................
.... 153
IV.
Conclusion...............................................................
........................................... 155

References...............................................................
.............................................. 155
I. Introduction
Catalysis of metalloporphyrins has attracted great attention in relation
to biological functions of hemoproteins. In 1979, lnoue and coworkers,1
in the course of their studies on chemical fixation of carbon dioxide
with metalloporphyrins, discovered a potential utility of
metalloporphyrins as catalysis (initiators) for controlled macromolecular
synthesis. Among a variety of metalloporphyrins, they studied compounds
with aluminum or zinc central metal ion as candidates for the chemical
fixation of carbon dioxide; this was done on the basis of (heir
successful development in 1968-1-of the alternating copolymerization of
carbon dioxide and three-membered cyclic ethers (epoxides) using
initiators composed of organoaluminum and organozinc compounds. In these
studies, they found that an aluminum tetraphenylporphyrin with axial
bound chloride. (TPP)AICI,
The Porphyrin Handbook
K.M. Kadish, K.M. Smith, R. Guilard, F_ds,
Volume 6 / Applications: Past, Present and Future
lc, brings about ring-opening polymerization of epoxides (11, Table 1) to
give polyethers with a narrow molecular weight distribution (MWD).
"Molecular weight" is an essential factor in affecting fundamental
properties of polymer materials. However, unlike some naturally occurring
macromolecules, such as proteins and nucleic acids, synthetic
macromolecules, except for those obtained by a stepwise approach, have a
broad MWD. In other words, they exist as mixtures of macromolecules with
different molecular weights (chain lengths). In general, the MWD is
caused by the heterogeneity of the growth of the polymer chain.
Figure I shows a schematic representation for addition polymerization
of unsaturated monomer (M) with initiator (1- ), where the chain growth
of a polymer molecule starts by the reaction of I- with M to generate an
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