| POLYMERS Vol.59 No.10 |
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COVER STORY
Frontier in Precision Polymerization |
| Growing Polymers: A Personal Account |
| Days with Cyclodextrins | Yasushi OKUMURA |
| <Abstract> Looking back at my research life, this essay traces the encounters with cyclodextrins and polyrotaxanes, the development of slide-ring gels, and the establishment of a venture company for commercialization of slide-ring materials involving many people, various support systems and investments. |
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| Research for Commercialization | Yuichi YAMAMURA |
| <Abstract> One of the missions of Mitsui Chemicals’ R&D program is to speed up the research and development and commercialization of products. To achieve this, inter-departmental cooperation is required. |
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| COVER STORY: Highlight Reviews |
| Stereospecific Living Coordination Polymerization of Propylene | Takeshi SHIONO and Zhengguo CAI |
| <Abstract> The
development of well-defined transition metal complexes for olefin polymerization
catalysis has resulted in a variety of unique living polymerization systems.
This article reviews new developments of stereospecific living polymerization
systems of propylene and their application to the synthesis of novel
block copolymers composed of stereoregular polypropylene sequences. However,
an equivalent amount of the transition metal complex to the number of
polymer chains is necessary in these living polymerizations. Recent advances
in the catalytic synthesis of monodisperse polyolefins and olefin block
copolymers, which can overcome this shortcoming of living polymerization,
are also described. Keywords: Ziegler-Natta Catalyst / Single-Site Catalyst / Living Polymerization / Stereospecific Polymerization / Propylene / Block Copolymer / Catalytic Polymerization |
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| Sequence Control in Radical Polymerization | Masami KAMIGAITO and Kotaro SATOH |
| <Abstract> Control
of monomer sequence is one of the ultimate goals of synthetic polymer
chemistry. This article introduces recent developments of sequence control
in radical polymerizations, such as precision synthesis of alternating
and gradient copolymers with controlled molecular weights by living radical
polymerization and sequence-regulated vinyl copolymers by metal-catalyzed
step-growth radical polymerization. Keywords: Radical Polymerization / Living Polymerization / Monomer Sequence / Alternating Copolymer / Gradient Copolymer / Vinyl Polymer |
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| Development of Polymerization in Asymmetric Liquid Crystal Reaction Field: Synthesis of Helical Polyacetylene and Precision Control of Its Helical Structure | Munju GOH and Kazuo AKAGI |
| <Abstract> Polymerization in an asymmetric reaction field using a chiral nematic
liquid crystal has been attracting current interests because it enabled
us to precisely control helical structures of conjugated polymers. This
article reviews recent advances and development of asymmetric polymerization
in chiral liquid crystal. Keywords: Conjugated Polymer / Helical Polyacetylene / Asymmetric Reaction Field / Chiral Nematic Liquid Crystal / Chiral Inversion / Hierarchical Structure / Binaphthyl Derivative / Cis-Rich Helical Polyacetylene |
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| COVER STORY:Topics and Products |
| Polymerization of Diazoacetates Initiated with Transition Metal Complexes | Eiji IHARA |
| <Abstract> High
molecular weight syndiotactic poly(ethoxycarbonylmethylenes) were prepared
by Rh-initiated polymerization of ethyl diazoacetate. (NHC) Pd/borate
systems were effective for the polymerization of diazoacetates with a
variety of ester groups. Keywords: Diazoacetate / Rh Complex / Pd Complex / Poly (Substituted Methylene) / Stereoselective Polymerization |
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| Emergence of Gelationous Chain Transfer Agents “RAFT Gel”s via Chemoselective Polycondensation | Akinori TAKASU and Ken YAMAMOTO |
| <Abstract> Scandium
trifluoromethanesulfonate [Sc(OTf)3]-catalyzed chemoselective
dehydration polycondensations of thiomalic acid (TMA) with several diols
afforded linear polyesters having pendant mercapto groups (Mn
> 1.0 × 104). We also demonstrated cross-linkings of the
pendent mercapto groups using thiocarbonyldiimidazole (TCDI) to prepare
gelationous chain transfer agents “RAFT Gel”s. Keywords: Polyester / Chemoselective Dehydration Polycondensation / Mercapto Group / Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization / Gelationous Chain Transfer Agents “RAFT Gel”s |
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| Controlled Isomerization Polymerization of Dienes and Cycloolefins: Synthesis and Aggregation Behaviors of the New Polymers | Daisuke TAKEUCHI and Kohtaro OSAKADA |
| <Abstract> Diimine
Pd complexes promote isomerization polymerization of 1,6-dienes and cyclopentenes
to result in polymers composed of cyclopentane and an oligomethylene
spacer. The isotactic polymers of 4-alkylcyclopentenes show liquid crystalline
properties. Keywords: Diene / Cycloolefin / Pd Complex / Isomerization Polymerization / Cyclopolymerization / Stereoselective Polymerization / Liquid Crystalline |
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| Precision Copolymerization of Epoxides with Carbon Dioxide | Koji NAKANO and Kyoko NOZAKI |
| <Abstract> Copolymerization
of propylene oxide (PO) with CO2 was investigated by using cobalt (III)
complexes bearing piperidinium end-capping arm (s). The catalyst system
can selectively produce poly (propylene carbonate) (PPC) even at complete
conversion of PO. Regio- and enantiomer-selective copolymerization resulted
in stereogradient-type PPC. Keywords: Epoxide / Carbon Dioxide / Copolymerization / Regioregularity / Stereoregularity |
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| Living Radical Polymerizations with Organic Catalysts | Atsushi GOTO |
| <Abstract> Living
radical polymerizations (LRPs) using organic (P, N, O, and C-centered)
catalysts were developed. The catalysts include such common compounds
as phosphites (P), amines (N), phenols (O), and dienes (C). Attractive
features of the LRPs include good environmental safety, low cost, and
robustness. Keywords: Living Radical Polymerization / Organic Catalysts / Phosphorus / Nitrogen / Oxygen / Carbon |
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| The Forefront of Materials Synthesized by Living Radical Polymerization | Takashi KAMESHIMA |
| <Abstract> The
polymers synthesized by living radical polymerization have a wide potential
application in various areas, and the recent progress of research has
enabled the polymerization method to be scaled up for commercial production. Living radical polymerization technology has the possibility to create a new business field by providing new functional materials. Keywords: Living Radical Polymerization / TERP / Block Copolymer / Nanotechnology / Pressure Sensitive Adhesives |
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| Covalent Dynamic Polymers Based on C=N Bonds in Imines and Hydrazones | Shunsuke FUJII and Takashi ONO |
| <Abstract> The
presented topics concern both basic and applied research on covalent
dynamic polymers based on C=N bonds in imines and hydrazones, capable
of responding to physical triggers or to chemical effectors by modification
of their very constitution, and thus constitute a new class of adaptive, “intelligent”
materials. Keywords: Dynamic Covalent Bonds / Dynamic Polymers / Adaptive Materials |
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| Front-Line Polymer Science |
| Role of Polymer Materials in Electronic Paper | Masayoshi HIGUCHI |
| <Abstract> Electronic
paper, which can hold images even after the power is turned off, has
received much attention as next generation’s display, because it will
contribute energy- and resource-saving. An electrophoretic style of electronic
paper is already commercially available as electronic books such as the
“Kindle™”, but now colorization of electronic paper is one of the
biggest topics. It is considered that an electrochromic style of electronic
paper
is a promising way to achieve the colorization. Many electrochromic materials
have been reported so far. Especially, organic-metallic hybrid polymers
formed by the complexation of metal ions as Fe(II) or Ru(II) with bis(terpyridine)
ligands have specific colors based on metal-to-ligand charge transfer
(MLCT) absorption and were revealed to show electrochromic properties
by electrochemical redox reactions of the metal ions. Multicolor electrochromic
change was also achieved by the introduction of two types of metal ions
into the polymer. New polymer materials such as organic-metallic hybrid
polymers may open the next door toward ultimate paper-like displays. Keywords: Electronic Papers / Electrochromic Properties / Organic-Metallic Hybrid Polymers / Metallo-Supramolecular Polyelectrolytes / Multicolor / Solid-State Devices / Smart Windows |
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