| POLYMERS Vol.61 No.11 |
| >> Japanese | >> English |
COVER STORY
New Developments in Polymer Reaction: from Precision Control to Material Design |
| COVER STORY: Highlight Reviews |
| Photoinitiated Click Reactions for the Creation of Spatially Defined Materials | Daigo MIYAJIMA, Masahito MURAI and Craig Jon HAWKER |
| <Abstract> Photoinitiated
click reactions possess significant advantages over traditional click
reactions as they allow for spatial and temporal control. This enables
the formation of patterned or gradient surfaces with specific substrates,
controlled attachment of biological entities, etc.. In this minireview,
we highlight the latest progress on photoinitiated click chemistry and
demonstrate the future potential of this emerging area. Keywords: Click Chemistry / Patterning / Photochemistry / Thiol-Ene / CuAAC / Polymer Chemistry / Materials Synthesis |
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| Synthesis and Application of Crosslinked Polymers with Degradable Property | Masamitsu SHIRAI |
| <Abstract> Cross-linked
polymers are widely used in industry because of their mechanical strength
and thermal stability. It is possible to develop new materials by adding
a degradable property to the cross-linked polymers. The cross-linked
polymers with degradable property have potentials as environmentally
friendly materials, highly functionalized materials, self-healing materials,
and so on. In this paper, the recent progress on the cross-lined polymers
with degradable property and their applications is reviewed. Keywords: Multifunctional Monomer / Crosslinked-Polymer / Degradation / Environmentally Friendly Materials / Reworkable Materials / Self-Healing |
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| Functionalization of Polysaccharides through Selective Derivatization | Atsushi OHNISHI, Tohru SHIBATA |
| <Abstract> The
derivatization of cellulose has two features, one being the intrinsic
reactivity of its three hydroxyl groups and the other the morphological
restriction. Cellulose solvents often help regioselective reactions by
removing the latter restriction. The hierarchical morphology of cellulose
can in reverse diversify the property of the product, e.g., preserving/dissolving microfibrils. In the latter part of this article, the syntheses of regioselective cellulose and amylose derivative with different substituents in relation to chiral recognition are introduced. Such a mixed derivative exhibited a chiral recognition different from either of the related trisubstituted with a single substituent while their averaged powers of chiral recognition were comparable. Keywords: Cellulose / Amylose / Regioselective / Substitution / Functionalyzation / Chiral Stationary Phase |
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| COVER STORY: Topics and Products |
| Precise Synthesis of Polymers End-Functionalized with Clickable Functional Groups and Their Application to Preparation of Functional Polymers | Toyoji KAKUCHI, Keita FUCHISE |
| <Abstract> The
combination of controlled/living polymerizations and click reactions
has realized the synthesis of polymers with various structures. Our group
has developed precise synthesis methods for polyester, polyether, poly(n-hexyl
isocyanate), and polyacrylamides end-functionalized with clickable functional
groups, such as an azido group, an ethynyl group, and so on. The end-functionalized
poly(N-isopropylacrylamide) and its block copolymer have been applied
to development of functional polymers. Keywords: Controlled/Living Polymerization / Click Reaction / End-Functionalized Polymers / Polyesters / Polyethers / Poly(n-hexyl isocyanate) / Polyacrylamides / Thermoresponsive Polymers |
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| Intermolecular Click and Intramolecular Clip Process for Constructing Multicyclic Polymer Topologies | Naoto SUGAI, Yasuyuki TEZUKA |
| <Abstract> Cyclic
and multicyclic polymers have gained increasing attention due to their
unique functions arisen from their topology effects. In this account,
a new synthetic protocol to construct complex multicyclic polymer topologies
is outlined by employing intermolecular click and intramolecular clip
process using a variety of cyclic or multicyclic precursors having prescribed
functional groups. A variety of complex polymer topologies has been constructed,
including bridge- and spiro- as well as fused-type tricyclic or tetracyclic
forms with programmed folding structures. Keywords: Cyclic Polymer / Topological Polymer Chemistry / Click Chemistry / Olefin Metathesis / Electrostatic Self-Assembly and Covalent Fixation |
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| Click Synthesis and Optoelectronic Properties of Novel Aromatic Polymers | Tsuyoshi MICHINOBU |
| <Abstract> p-Type
semiconducting polymers were post-functionalized by the click chemistry-type
addition reaction between electron-rich alkynes and acceptor molecules.
For example, the addition of tetracyanoethylene (TCNE) to aromatic polyamines
bearing electron-rich alkynes formed donor-acceptor chromophores with
low energy charge-transfer bands. Electrochemistry measurements revealed
that the polymer energy levels decreased as more TCNE were added. The
thin film transistors of these polymers were fabricated, and it was demonstrated
that there is a clear correlation between the polymer energy levels and
hole mobilities. Keywords: Click Chemistry / Donor-Acceptor Systems / Charge-Transfer / Aromatic Polymers / Electrochemistry / Mobility / Thin Film Transistor |
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| Addition of Photosensitivity to Engineering Plastics Utilizing Polymer Reaction: Reaction Development Patterning | Toshiyuki OYAMA |
| <Abstract> Conventional
photosensitive polymides (PSPIs) have disadvantages such as necessity
of high temperature post-curing after pattern formation due to their
use of polyimide precursors, poly(amic acid)s, as polymer components.
We have developed a novel mechanism, reaction development patterning
(RDP), to give photosensitivity to polyimides and other engineering plastics.
Pattern formation by RDP is based on selective change in solubility of
engineering plastics at photo-irradiated (or unirradiated) areas by nucleophilic
acyl substitution between carboxylic-acid derivatives in a polymer chain
and nucleophiles in a developer during development process. Thus, RDP-based
PSPIs are obtained from polyimides themselves, and pattern formation
from polycarbonates and polyesters is also achieved by papplying RDP
to these polymers. Keywords: Photosensitive Polyimide / Photosensitive Engineering Plastics / Nucleophilic Acyl Substitution / Diazonaphthoquinone / Development by Alkaline Solution |
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| Development of Dismantlable Adhesion Materials Based on Design of Polymer Reactions | Akikazu MATSUMOTO |
| <Abstract> We
have demonstrated the validity of a new type of pressure-sensitive adhesion
system using block copolymers containing the low glass transition poly(2-ethylhexyl
acrylate) or poly(n-butyl
acrylate) segment and the reactive poly(tert-butyl acrylate) (PtBA) segment
in the presence of a photoacid generator. This adhesion system can be
easily debonded due to a change
in the polymer properties of the adhesives by acid-catalyzed deprotection
uniquely occurring during the photoirradiation followed by postbaking.
The block copolymers with a well-defined molecular structure were synthesized by living radical polymerization, such as atom transfer radical polymerization and organotellurium-mediated living radical polymerization and their adhesive properties were evaluated using the 180・peel test. A drastic change in the adhesive strength of the block copolymers was observed in response to the dual external stimuli consisting of UV irradiation and the subsequent heating. Keywords: Block Copolymer / Controlled Polymerization / Deprotection / Dismantalble Adhesion / Living Radical Polymerization / Photoacid Generator / Polyacrylate / Pressure-Sensitve Adhesive |
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| Front-Line Polymer Science |
| Development of Inorganic Polymers: To Inorganic-Element-Block Polymers | Kensuke NAKA |
| <Abstract> Thanks
to meet organic-inorganic polymer hybrids with recent development of
nano-sized inorganic blocks, single component polymer hybrids or matrix-free
nanocomposites have been proposed. This kind of materials is regarded
as “Inorganic-element-block polymers”, which is an extended concept
of “organic-inorganic hybrid polymers”. This review describes recent
development of the Inorganic-element-block polymers, mainly focusing
on the synthesis
of polyhedral oligosilsesquioxane
derivatives and their solid-state properties. Examples of inorganic
nanoparticle hybrids are also introduced. Keywords: Inorganic-Element-Block Polymers / Single Component Polymer Hybrids / Matrix-Free Nanocomposites / Polyhedral Oligosilsesquioxane / Inorganic Nanoparticle Hybrids / Inorganic Polymers / Organic-Inorganic Hybrids |
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| Polymer Science and I: A Personal Account |
| As a Professional Researcher | Tomoyasu HIRAI |
| <Abstract> I would like to contribute substantially to the society, on the basis of my skills and the knowledge that I have gained. |
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