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Kim, Young Yong,Jung, Sungmin,Kim, Changsub,Ree, Brian J.,Kawato, Daisuke,Nishikawa, Naoki,Suemasa, Daichi,Isono, Takuya,Kakuchi, Toyoji,Satoh, Toshifumi,Ree, Moonhor American Chemical Society 2014 Macromolecules Vol.47 No.21
<P>A series of miktoarm star polymers, [poly(<I>n</I>-hexyl isocyanate)(12K)]–[poly(ε-caprolactone)<SUB>1–3</SUB>(5K)] (PHIC–PCL<SUB>1–3</SUB>) (composed of a rigid self-assembling PHIC arm and one to three flexible crystallizable PCL arms), were investigated to examine the polymers’ thermal properties and nanoscale thin film morphologies. The miktoarm polymers were stable up to 180 °C. The PHIC and PCL arm components underwent phase separation during the solution casting, drying, and post toluene-annealing processes, forming interesting but very complex thin film morphologies. The resulting thin film morphologies were examined in detail for the first time using synchrotron grazing incidence X-ray scattering (GIXS) measurements and quantitative data analysis. All of the miktoarm star polymer films formed vertically well-oriented lamellar structures, regardless of the number and length of PCL arms. These structures were quite different from the cylindrical structures commonly observed in conventional flexible diblock copolymer films having comparable volume fractions. The individual PHIC and PCL lamellar domains self-assembled to form their own respective morphological structures. The PHIC lamellae consisted of a mixture of horizontal and vertical multibilayer structure domains, as observed in the PHIC homopolymer film. The PCL lamellae formed fringed micelle-like crystals and/or highly imperfect folded crystals that differed significantly from the structures found in a PCL homopolymer film composed of typical folded lamellar crystals. These PCL crystals were formed with a mixture of vertical and horizontal orthorhombic lattices. Overall, the GIXS analysis revealed that the parameters that characterized the hierarchical structures in the thin films depended significantly on the number and length of the PCL arm and its crystallization characteristics as well as the chain rigidity and multibilayer structure formation characteristics of the PHIC arm.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/mamobx/2014/mamobx.2014.47.issue-21/ma501695b/production/images/medium/ma-2014-01695b_0011.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ma501695b'>ACS Electronic Supporting Info</A></P>
Phinjaroenphan, Rarm,Kim, Young Yong,Ree, Brian J.,Isono, Takuya,Lee, Jinseok,Rugmai, Supagorn,Kim, Heesoo,Maensiri, Santi,Kakuchi, Toyoji,Satoh, Toshifumi,Ree, Moonhor American Chemical Society 2015 Macromolecules Vol.48 No.16
<P>Two series of crystalline-crystalline miktoarm star polymers were prepared and their thin film morphologies were investigated in detail by synchrotron grazing incidence X-ray scattering (GIXS): poly(n-hexyl isocyanate)(5000) poly(epsilon-caprolactone) (1-3)(17000) (PHIC(5k)-PCL1-3(17k)) and poly(n-hexyl isocyanate) (10000) poly(epsilon-caprolactone)(1-3)(10000) (PHIC(10k)-PCL1-3(10k)). In addition, their thermal properties were examined. All miktoarm star polymers revealed a two-step thermal degradation behavior where the PHIC arm was degraded first, followed by the PCL arm underwent degradation. Interestingly, all miktoarms were found to show a highly enhanced thermal stability, regardless of their molecular weight over 3k to 17k, which might be attributed to their one-end group capped with the counterpart arm(s) via arm-joint formation. Surprisingly, all miktoarm star polymers always developed only lamellar structure in toluene- and chloroform-annealed films via phase-separation, regardless of the length of PHIC arm as well as the length and number of PCL arm. Despite having highly imbalanced volume fractions, lamellar structure was constructed in the films of miktoarm star polymers through the override of volume fraction rule based on the rigid chain properties, self-assembling characteristics, conformational asymmetry, and compressibilities of PHIC and PCL arms. Furthermore, the orientation of such lamellar structures was controlled by the selection of either toluene or chloroform in the solvent-annealing process. The PHIC arm phases in the lamellar structures favorably formed a mixture of edge-on and face-on structures with fully extended backbone and bristle conformations even under the confined lamellar geometry and arm-joint. The PCL arm phases still crystallized, forming fringed-micelle like structures in which orthorhombic crystals were laterally grown along the in-plane direction of lamellae although their crystallization was somewhat suppressed by the confined lamellar geometry and arm-joint. Overall, crystalline-crystalline PHIC-PCL1-3 miktoarm polymers demonstrated very interesting but unusual, very complex hierarchical structures in the solvent-annealed thin films.</P>
Zhengguo Gao,Qian Duan,Jinaying Liang,Xiangdong Tao,Yuan Cui,Toshifumi Satoh,Toyoji Kakuchi 한국고분자학회 2012 Macromolecular Research Vol.20 No.5
Zinc(II) tetra-(2-chloropropionylamido) phthalocyanine (TAPcCl) was synthesized as the initiator for atom transfer radical polymerization (ATRP). Using CuBr/tris(2-dimethylaminoethyl)amine as the catalyst system,ATRP of N-isopropylacrylamide (NIPAM) was performed to create a new star-shaped poly(N-isopropylacrylamide)(PNIPAM) with a zinc phthalocyanine core and PNIPAM arms (TAPc-PAM). The structures of the initiator and the polymers were characterized by means of Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. The polydispersity index obtained by gel permeation chromatography indicated that the molecular weight distribution was narrow. The lower critical solution temperatures (LCST) for the TAPc-PAM aqueous solutions measured using the turbidimetry method were increased due to incorporation of the phthalocyanine core and decreased as molecular weight increased. TAPc-PAM possessed photocatalytic activity, a finding that was verified by Rhodamine B degradation in the presence of hydrogen peroxide under visible light. Moreover, the catalytic efficiency was higher at its LCST, which encouraged reuse of the photocatalyst.
Satoh, T.,Nishikawa, N.,Kawato, D.,Suemasa, D.,Jung, S.,Kim, Y.,Ree, M.,Kakuchi, T. Royal Society of Chemistry 2014 Polymer chemistry Vol.5 No.2
Well-defined hydroxyl end-functionalized poly(n-hexyl isocyanate), PHIC-(OH)(2) and PHIC-(OH)(3), as rod-type macroinitiators were synthesized by the Cu-catalyzed azide-alkyne cycloaddition reactions of azido end-functionalized PHIC with ethynyl alcohol derivatives. The PHIC-(OH)(2) and PHIC-(OH) 3 were suitable macroinitiators for the ring-opening polymerization of L-LA and epsilon-CL leading to the synthesis of novel rod-coil type miktoarm star copolymers, PHIC-b-PLLA(2), PHIC-b-PLLA(3), PHIC-b-PCL2, and PHIC-b-PCL3, with controlled molecular weights, narrow polydispersities, and controlled arm numbers. Additionally, the thermal and solution properties of the obtained miktoarm star copolymers along with the corresponding block copolymers, PHIC-b-PLLA and PHIC-b-PCL, were characterized by TGA, DSC, and DLS analyses.