Polymer Journal - Vol. 37, No. 8 (August, 2005)

Polymer Journal
Vol. 37, No. 8 (August, 2005)

[Regular Article] Web Release Date: August 15, 2005

545-549 Diphenyliodonium Salts with Pyranine Conk as an Environment-friendly Photo-acid Generator and Their Applications to Chemically Amplified Resists
N. Tarumoto, N. Miyagawa, S. Takahara, and T. Yamaoka
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A new environment-friendly PAG with a non-mutagenic dye was designed. The Ames test indicated the PAG of tris(diphenyliodonium) 9-hydroxy-pyrene-1,4,6-trisulfonate to be non-mutagenic. The thermal stability of PAG was adequate for use as a chemically amplified resist. The photo-acid generating efficiency in a polymer with a t-buthoxycarbonyl protecting group was 31 mJ/cm² (365 nm) and 58 mJ/cm² (405 nm). The PAG has sufficient potential for use as a chemically amplified resist.

[Regular Article] Web Release Date: August 15, 2005

550-559 Isothermal Crystallization of Poly(ethylene-co-glycidyl methacrylate)/Silica Nanocomposites
J.-W. Huang, C.-C. Kang, and T.-H. Chen
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A TEM photomicrogragh showed that nano-sized silica particles modified by γ-aminopropyltriethoxysilane were more compatible with a poly(ethylene-co-glycidyl methacrylate) (PEGMA) matrix and better dispersed therein. The modified particles may affect the isothermal crystallization of PEGMA.

[Regular Article] Web Release Date: August 15, 2005

560-564 Phase Separation and Dewetting Induced Surface Pattern in PS/PMMA Blend Films
X. Rui, Z. Song, S. Jing, and T. Decheng
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This paper report the pattern evolution of phase separation and dewetting of PS/PMMA blend thin films at 160 °C. The cross-section of the AFM image after selective removal of the PS component is reported for the first time. A trench was observed inside and outside the PMMA rim, respectively. It demonstrates that the PS component extends considerably into the PMMA substrate layer, and confirms the notion of a deformable interface between the two materials.

[Regular Article] Web Release Date: August 15, 2005

565-570 pH and Temperature-sensitive Behaviors of Poly(4-vinyl pyridine-co-N-isopropyl acrylamide) Microgels
K. S. Kim and B. Vincent
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Poly(4VP-co-NIPAM) microgels were prepared from 4-vinyl pyridine (4VP) and N-isopropyl acrylamide (NIPAM) with methylene-bis-acrylamide (MBAm) as a cross-linking agent using partially quarternized poly(4-vinyl pyridine, P4VP) as emulsifier, which is a special emulsion polymerization method. The morphology and hydrodynamic diameter of the microgel particles were characterized by TEM and photon correlation spectroscopy (PCS). The dependence of pH and temperature of the copolymer microgel particles were investigated. As results, the influence of the KCl concentration in the microgel dispersion was observed.

[Regular Article] Web Release Date: August 15, 2005

571-577 Binding of Bile Salts to an Amphiphilic Polysulfonate Modified with Cholesterol Moieties
S. Yusa, K. Ikeda, T. Yamamoto, and Y. Morishima
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Interactions of sodium cholate (SC) with intermolecularly bridged flower micelles formed from cholesterol-bearing amphiphilic polyelectrolytes were investigated by ¹H NMR relaxation time, static light scattering, quasi-elastic light scattering, and fluorescence techniques. The hydrophobic microdomains formed from the pendent cholesteryl groups of the amphiphilic polyelectrolytes were disrupted by the addition of SC in water. It is suggested that the cholesterol-bearing amphiphilic polyelectrolytes act as an adsorbent for SC in ileum.

[Regular Article] Web Release Date: August 15, 2005

578-583 Enhanced Stereocontrol in Disyndiotactic-specific Group Transfer Polymerization of Methyl Crotonate—Stereochemical Evidence of Group Transfer
K. Ute, T. Tarao, and T. Kitayama
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Group transfer polymerization (GTP) of methyl crotonate was examined by using a ketene silyl acetal with tert-butyldimethylsilyl group in the presence of HgI₂ and tert-butyldimethylsilyl iodide. Under optimized conditions, the GTP produced disyndiotactic polymers with narrow molecular weight distribution in quantitative yields. The trialkylsilyl group was found to exert control over the stereochemical process of the GTP; the bulky tert-butyldimethylsilyl group leads to much higher disyndiotacticity than trimethylsilyl and triethylsilyl groups, providing a direct evidence for the transferring silyl group to be involved in the propagation steps.

[Regular Article] Web Release Date: August 15, 2005

584-591 Effects of Phase Separation on the Crystallization Behavior in a Binary Blend of Poly(ε-caprolactone) Homopolymer and Poly(ε-caprolactone)-block-Polybutadiene Copolymer
M. Akaba and S. Nojima
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The crystallization process of poly(ε-caprolactone) (PCL) chains in a binary blend of PCL homopolymer and PCL-block-polybutadiene diblock copolymer (PCL-b-PB), where the temperature range of an UCST-type phase separation overlaps with that of crystallization, has been investigated by synchrotron small-angle X-ray scattering as a function of the characteristic length of composition variation ξ formed by the phase separation between components. When ξ<500 nm the crystallization rate of PCL is equal to that of PCL blocks in PCL-b-PB, while when ξ>500 nm the crystallization rate of PCL deviates significantly from that of PCL blocks, and they approach to the values of neat polymers with increasing ξ (Figure).

[Regular Article] Web Release Date: August 15, 2005

592-598 A Helical Ladder Polymer: Synthesis and Magnetic Circular Dichroism of Poly[phenylene-4,6-bis(methylsulfonio)-1,3-diyl triflate]
T. Iwasaki, K. Katayose, Y. Kohinata, and H. Nishide
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A helical ladder polymer composed of a fused benzothiophenium ring was synthesized via the intramolecular ring-closing reaction of the methylsulfoxide-substituted poly(1,3-phenylene). The precursor polymer was prepared by the palladium-catalyzed polymerization of 1,3-dibromobenzene and 1,3-phenylenebisborate and the following quantitative oxidation. The intramolecular ring-closing of the precursor polymer yielded poly[phenylene-4,6-bis(methylsulfonio)-1,3-diyl triflate]. The obtained polymer is one of the new poly(thiaheterohelicne)s. Magnetic circular dichroism of the polymer suggested both a helical structure and an electron transition ascribed to the fused ring structure.

[Regular Article] Web Release Date: August 15, 2005

599-607 Photoresponsive Change of the Surface Potential Generated by Helical Peptide Self-Assembled Monolayers
Y. Tada, T. Morita, J. Umemura, M. Iwamoto, and S. Kimura
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Photoresponsive helical peptides, which are composed of two helical peptide segments with an intervening azobenzene unit, were synthesized, and the self-assembled monolayers (SAMs) of the peptides were formed on gold. The molecular orientation changed reversibly upon UV and visible light irradiation due to photoisomerization of the azobenzene unit. The movement of the helices in the helical peptide SAMs were suggested to occur in a cooperative manner. Upon photoirradiation, the reversible change of the surface potential was observed.

[Regular Article] Web Release Date: August 15, 2005

608-616 Polymerization of Substituted Acetylenes by the Grubbs–Hoveyda Ru Carbene Complex
T. Katsumata, M. Shiotsuki, S. Kuroki, I. Ando, and T. Masuda
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Polymerization of various mono- and disubstituted acetylenes was investigated by using Grubbs–Hoveyda catalyst (1). Among the monomers examined, hexyl propiolate (2) and 1-phenyl-2-(p-trimethylsilyl)phenylacetylene (3) polymerized in moderate yields. Ru-based poly(2) possessed relatively high cis content (75%) according to NMR. Ru-based poly(3) displayed a narrower conjugation than those obtained with other catalysts. The ¹³C NMR spectra of this polymer in solid and solution states showed quite different signal patterns from those with conventional catalysts, suggesting a different geometric structure of main chain.

[Regular Article] Web Release Date: August 15, 2005

617-624 Graft Polymerization of Styrene and Acrylates on the Prepolymer Having TEMPOL Residues
Y. Miura, Y. Isobe, T. Nakamura, M. Sugiura, and Y. Okamoto
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Using living radical polymerization, graft polymers consisting of a poly(methyl methacrylate) main chain and side chains composed of various monomers, such as styrene and n-butyl acrylate, were synthesized. The polymers had a narrow polydispersity. Especially, for the graft polymerization of acrylates, the addition of a small amount of TEMPOL to the polymerization system on the side chain improved the livingness of the polymerization. The effect of added free TEMPOL was also studied on the homopolymerization of n-butyl acrylate using an initiator bearing a TEMPOL residue.

[Note] Web Release Date: August 15, 2005

625-628 Oxidative Coupling Polymerization of Silicon-Tethered p-Alkoxyphenol Derivatives with CuCl(OH)-N,N,N',N'-Tetramethylethylenediamine Catalyst
S. Habaue, M. Ohnuma, M. Mizoe, and T. Temma
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Novel bifunctional p-alkoxyphenol derivatives were polymerized with the conventional copper(II) catalyst at room temperature under an O₂ atmosphere to preferentially afford a polymer having a polyphenylene structure, whereas the oxidative coupling polymerization of p-alkoxyphenol gave a polymer rich in the oxyphenylene unit.

Web Release Date: August 15, 2005

629-632 Asymmetric Radical Polymerization of N-Phenylmethacrylamides
Y. Amano and Y. Okamoto
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We, for the first time, succeeded in obtaining optically active polymers through the asymmetric radical polymerizations of 2,6-disubstituted N-phenylmethacrylamide derivatives in optically active solvents, such as (+)- and (−)-menthol. The polymers were not soluble in organic solvents, but clearly showed CD peaks when dispersed in liquid paraffin. However, the poly(N-phenylmethacrylamide)s prepared from monomers without two substituents at both 2- and 6-positions exhibited no CD absorption in the solid state. The chiral structure was constructed only from the 2,6-disubstituted N-phenylmethacrylamides and was stably maintained in the solid state even at rather high temperatures.

Web Release Date: August 15, 2005

633-635 Anti-deterioration Effect of Lignin as an Ultraviolet Absorbent in Polypropylene and Polyethylene
K. Toh, S. Nakano, H. Yokoyama, K. Ebe, K. Gotoh, and H. Noda
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The anti-deterioration effect of lignin was estimated by measuring change in yield strength (yield strength retention rate) after outdoor exposure. The yield strength retention rate of the polypropylene with lignin was significantly higher than those of test pieces without lignin (Figure,

, 0% lignin;

, 1% lignin. Values are mean ± standard error obtained from five independent measurements.). These findings indicate that lignin is effective as an ultraviolet absorbent for these two resins.