Polymer Journal
Vol. 41, No. 8 (August, 2009)

[Award Accounts: SPSJ Hitachi Chemical Award Accounts] Web Release Date: June 24, 2009

569-581 Development of Novel Photo-Functional Materials Based on Cyclic Oligomers  H. Kudo and T. Nishikubo [Full Text PDF(J-STAGE)]

Novel photo-functional materials, refractive-index-changing materials, argon fluoride (ArF) resist materials, and electron beam (EB) resist materials, were designed based on calixarenes, cyclodextrin, and noria. The changes of refractive index of calixarene derivatives with photo-reactive groups were in the range from 0.007 to 0.061 in thin films. ArF resist using a β-CD derivative provided a clearly resolved 100 nm line and space pattern. EB resist using noria derivatives provided clear line and space patterns at resolutions of 70 and 50 nm.

[Short Communication] Web Release Date: June 3, 2009

582-583 Detection of Poorly-Oriented Component in Uniaxially Stretched Poly(glycolic acid) Fiber Studied Using 13C Solid-State NMR  S. Sekine, W. Sakiyama, K. Yamauchi, and T. Asakura [Full Text PDF(J-STAGE)]

13C CP NMR spectra of uniaxially oriented poly(glycolic acid) PGA fibers were obtained as a function of the angle of the PGA fiber axis and external magnetic field. With increasing the stretching ratio of the fiber, a remarkable sharpness at the lower field region was observed between 2.0 and 2.5 times. This is due to change in the poorly-oriented components in the PGA samples.

[Short Communication] Web Release Date: June 10, 2009

584-585 Synthesis of Novel Poly(tetramethyl-2,7-silpyrenylenesiloxane) and Its Thermal and Optical Properties  K. Imai, T. Sasaki, J. Abe, A. Kimoto, Y. Tamai, and N. Nemoto [Full Text PDF(J-STAGE)]

Novel poly(tetramethyl-2,7-silpyrenylenesiloxane) (P1) was obtained by polycondensation of a novel disilanol monomer, i.e., 2,7-bis(dimethylhydroxysilyl)pyrene (M1). The temperature at 5% weight loss (Td5) of P1 was 519 °C, indicating the good thermostability of P1. The fluorescence quantum yields of M1 and P1 in chloroform solution were 0.49 and 0.39, respectively, and much larger than that of pyrene. The emission from P1 was mainly resulted from the excimers, possibly owing to intra- and/or inter-molecular interactions between the pyrenylene moieties in P1.

[Short Communication] Web Release Date: June 24, 2009

586-587 Novel Shape Memory Using Delay and Thermal Hysteresis of Crystalline Phase Transition in Cross-Linked Polybutylene Succinate  K. Inoue and M. Yamashiro [Full Text PDF(J-STAGE)]

Cross-linked PBS with polyisocyanate was synthesized, which has an attractive shape-memory performance: that is easy deformation at room temperature and heat resistance of deformed shape. We discovered the contrary characters are realized by delay and thermal hysteresis of crystalline phase-transition. The delay and hysteresis are caused by hydrogen bonding between urethane functions and 3D network structure. This shape memory polymer enables easy fitting to human body without burning.

[Regular Article] Web Release Date: June 10, 2009

588-594 Dipole Moment of Poly(ethylene oxide) in Solution and Its Dependence on Molecular Weight and Temperature  N. Yamaguchi and M. Sato [Full Text PDF(J-STAGE)]

The dipole moment of poly(ethylene oxide) (PEO) and its dependence on molecular weight and temperature is investigated by measuring the dielectric constant and density of PEO-benzene solutions in the temperature from 25 to 55 °C. The dipole moments of the PEO polymers ‹μmolecule2›1/2, increased linearly with the square root of the degree of polymerization n. The following dipole moment ratio and temperature coefficient were obtained: ‹μ2›/m2 = 0.472 ± 0.002 (25 °C) and dln‹μ2›/dT = (2.11± 0.28)× 10−3 K−1.

[Regular Article] Web Release Date: June 3, 2009

595-603 Mn2(CO)10-Induced RAFT Polymerization of Vinyl Acetate, Methyl Acrylate, and Styrene  K. Koumura, K. Satoh, and M. Kamigaito [Full Text PDF(J-STAGE)]

A dinuclear manganese complex [Mn2(CO)10] induced the controlled/living radical polymerization of vinyl acetate, methyl acrylate, and styrene in conjunction with dithiocarbonyl compounds [R–SC(S)Z] under weak visible light at 40 °C. The obtained polymers had controlled molecular weights, narrow molecular weight distributions, and well-defined chain-end groups originating from R–SC(S)Z. The polymerization most probably proceeds via the reversible activation of the C–SC(S)Z bond by ·Mn(CO)5 via the metal-catalyzed process and/or by the carbon-centered radical species via the addition-fragmentation chain transfer (RAFT) process.

[Regular Article] Web Release Date: June 10, 2009

604-608 Novel Partial Esterification Reaction in Poly(amic acid) and Its Application for Positive-Tone Photosensitive Polyimide Precursor  M. Tomikawa, S. Yoshida, and N. Okamoto [Full Text PDF(J-STAGE)]

We found novel partial esterification in poly(amic acid) (PAA) by reacting with N,N-dimethylformamide dialkyl acetals. The reaction proceeded quantitatively under mild condition without any catalysis. The partial esterification allowed us to control the solubility of PAA to alkaline solutions strictly. Positive-tone photosensitive polyimide (posi PSPI) was prepared by mixing with the partially esterifed PAA and diazonaphthoquinone compound. The posi PSPI obtained in this work was easy to prepare.

[Regular Article] Web Release Date: June 3, 2009

609-615 9,9-Diarylfluorene-Based Poly(alkyl aryl ether)s: Synthesis and Property  H. Hayashi, M. Takizawa, T. Arai, K. Ikeda, W. Takarada, T. Kikutani, Y. Koyama, and T. Takata [Full Text PDF(J-STAGE)]

Polyethers possessing 9,9-diarylfluorene moiety (F-PEs) were synthesized by the polycondensation of 9,9-bis(hydroxyaryl)fluorenes with alkyl ditosylates. The F-PEs showed good solubility, thermal property, and water-resistance, while the refractive index values were in a range of 1.62–1.66 and the birefringence was very low. The carbon filler dispersing ability using C60 was also investigated.

[Regular Article] Web Release Date: June 10, 2009

616-621 Dielectric Properties of Polyethylene Oxide Doped with NH4I Salt  A. S. Ayesh [Full Text PDF(J-STAGE)]

Permittivity data (ε′) was fitted in the frequency domain at room temperature using Yan and Rhodes model in order to estimate the relaxation times for PEO/NH4I electrolytes. Due to the excellent fitting obtained using this model, PEO/NH4I electrolytes can be presented in equivalent circuit as RC in parallel circuits connected in series Correlations between dielectric parameters and thermal analysis is reported. This study shows that the relaxation process of these electrolytes is due to viscoelastic relaxation.

[Regular Article] Web Release Date: June 17, 2009

622-628 Characterization of the Microstructure of Bimodal HDPE Resin  Y. Fan, Y. Xue, W. Nie, X. Ji, and S. Bo [Full Text PDF(J-STAGE)]

Two industrial bimodal HDPE resins, having similar molecular weight, molecular weight distribution, and short-chain branching content but different mechanical properties, were fractionated through cross-fractionation (Preparative Solution Crystallization Fractionation and Solvent Gradient Fractionation). The results indicate that most of the branches fall into the high molecular weight chains in both low-temperature fractions of Preparative Solution Crystallization Fractionation. However, the high molecular weight chains in the low-temperature fraction of resin A contain less SCB than that of resin B.

[Regular Article] Web Release Date: June 24, 2009

629-633 Electro-Induced Early Transition Metal Metathesis Catalyst Systems for the Production of Polyacetylene  S. Karabulut [Full Text PDF(J-STAGE)]

1,3,5,7-cyclooctatetraene (COT) was polymerized via ring opening metathesis polymerization with the use of electro-induced Mo and W-based catalysts The soluble and conjugated polyacetylene (PA) was obtained. The polymer product has been characterized by solution phase spectroscopic methods including NMR, IR, UV-visible and DSC.

[Regular Article] Web Release Date: June 17, 2009

634-642 Silane-Bridged Electroless Ni-Plating on Submicron Polymer Spheres  W.-C. Liaw, P.-C. Huang, K.-P. Chen, and C.-S. Chen [Full Text PDF(J-STAGE)]

Silane coupling agent (3-trimethoxysilyl propryl methacrylate) was used to functionalize the surface of submicron polymer spheres (sized 168–650 nm) for bridging the polymer core (polystyrene crosslinked with divinylbenzene) and the metal coating shell. The silane bridge was proven to be more durable than the case of carboxylic acid group. Besides bridging with the metal coating, neighboring silyl groups also form Si-O-Si 2-dimensional network by condensation between two Si-OHs, which further stabilized the bondage between the polymer core and the metal shell.

[Regular Article] Web Release Date: June 17, 2009

643-649 Synthesis and Properties of Addition-Type Poly(norbornene)s with Siloxane Substituents  H. Tetsuka, K. Isobe, and M. Hagiwara [Full Text PDF(J-STAGE)]

Novel poly(norbornene)s with oligosiloxane groups were synthesized via vinyl addition polymerization route. The obtained polymers showed good solubility in common organic solvents and very high Tg up to 265 °C, depending on the content and structure of the siloxane groups. The incorporation of siloxane groups in the chain resulted in significant increase in the mechanical flexibility of their films. In addition, the gas permeation properties of these new polymers were investigated.

[Regular Article] Web Release Date: June 17, 2009

650-660 Synthesis of Degradable Materials Based on Caprolactone and Vinyl Acetate Units Using Radical Chemistry  S. Agarwal, R. Kumar, T. Kissel, and R. Reul [Full Text PDF(J-STAGE)]

Radical ring-opening copolymerization of 2-methylene-1,3-dioxepane (MDO) with vinyl acetate provided successfully degradable materials with ester units onto the C-C backbone of poly(vinyl acetate). The material properties like glass transition temperature and mechanical properties can be controlled by changing the amount of comonomers in a simple way. The degradation products were found to be non-toxic.

[Regular Article] Web Release Date: June 17, 2009

661-666 Effect of Blended Ionomers on the Strain Hardening of Polyester-Type Elastomer/Ionomer Blends  A. Nishioka, S. Onodera, T. Koda, K. Miyata, K. Furuichi, K. Kodama, and K. Koyama [Full Text PDF(J-STAGE)]

A poly(ethylene-co-methacrylic acid) (EMMA) based Na ionomer was blended with thermoplastic polyester elastomer (TPEE), and the effect on the uniaxial elongational viscosity was investigated. The effect of the degree of neutralization (ND) of EMAA-Na on strain hardening of TPEE/ionomer blends was estimated. Strain hardening of TPEE under uniaxial elongation was effective using an ionomer with ND above 40% for a TPEE/EMAA-Na blend ratio of 80/20 wt %.

[Regular Article] Web Release Date: June 24, 2009

667-671 The Effects of Interfacial Tensions of Amphiphilic Copolymers on Honeycomb-Patterned Films  M. Kojima, Y. Hirai, H. Yabu, and M. Shimomura [Full Text PDF(J-STAGE)]

Honeycomb-patterned films were prepared by casting chloroform solutions of polystyrene and amphiphilic copolymers, which were synthesized from hydrophobic monomer and hydrophilic monomer at various copolymerization ratios. Uniformity of micropores of the honeycomb-patterned film increased with decreasing the value of the interfacial tension between water and chloroform solution of amphiphilic copolymer. Moreover, polymer frame of honeycomb-patterned film became thinner with decreasing the value of the interfacial tension.

[Regular Article] Web Release Date: June 24, 2009

672-678 Polymerization of Methyl Methacrylate with Radical Initiator Immobilized on the Inside Wall of Mesoporous Silica  K. Ikeda, M. Kida, and K. Endo [Full Text PDF(J-STAGE)]

The polymerization of MMA with ACP-MCM-41 proceeded to give high-molecular weight polymers. The termination reactions of the propagating radicals were extremely suppressed by movement restriction of the polymer chains covalently immobilized on the inside wall of MCM-41 in the polymerization of MMA initiated at the inside wall of MCM-41. The presence of super long-lived propagating radical on the inside wall of MCM-41 was confirmed by ESR measurement, post-polymerization and block copolymerization with styrene.

[Regular Article] Web Release Date: June 24, 2009

679-684 Development of a Highly Oriented Poly-biphenylenebisoxazole Fiber Obtained via a Precursor Polymer Spun From a Liquid Crystalline Aqueous Solution  M. Chokai, D. Wilbers, B. Nagasaka, H. Kuwahara, T. de Weijer, E. Klop, T. Hayakawa, and M. Kakimoto [Full Text PDF(J-STAGE)]

A new lyotropic aqueous solution of poly(3,3′-dihydroxybenzidine terephthalamide) (DHBTA) can be formed into a polyhydroxyamide fiber by a wet spinning process. The resulting fiber has higher orientation and better mechanical properties than a polyhydroxyamide fiber spun from an isotropic solution. The polyhydroxyamide fiber was converted successfully into a poly-biphenylenebisoxazole (biPBO) fiber by a heat treatment process. The novel process allows the spinning of a bisoxazole fiber with promising mechanical properties without using corrosive sulfuric acid, phosphoric acid or organic solvents.

[Note] Web Release Date: June 17, 2009

685-690 Amphiphatic Piperazine, Pyrazine, and Pyridine Derivaties as the Thermal Latency for Epoxy-Phenolic Resins  K.-L. Chen, H.-C. Lin, C.-S. Huang, Y.-H. Shen, J.-J. Huang, and F. F. Wong [Full Text PDF(J-STAGE)]

Novel amphiphatic piperazine, pyrazine, and pyridine compounds were evaluated as thermal latent catalysts for the polymerization of diglycidyl ether of bisphenol A (DGEBA). Results including the viscosity-storage time, cure activation energy, exothermic heats and viscosity-storage time obtained indicated that the amphiphatic piperazine, pyrazine, and pyridine compounds exhibited good to excellent latency properties at room temperature.