Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 21

1 November 2005

Volume 43, Issue 21

Pages 4981–5346

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      Metallosupramolecular approach toward functional coordination polymers (pages 4981–4995)

      Rainer Dobrawa and Frank Würthner

      Version of Record online: 13 SEP 2005 | DOI: 10.1002/pola.20997

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      Coordination polymers constructed by a supramolecular approach from different metal ions and pyridine–ligand systems are highlighted, and their applications as functional materials for artificial membrane and enzyme models, responsive gels, light-harvesting systems, and organic light-emitting diodes are discussed on the basis of individual examples.

  2. Articles

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    1. A novel tridentate nitrogen donor as ligand in copper catalyzed ATRP of methyl methacrylate (pages 4996–5008)

      Anuj Mittal and Swaminathan Sivaram

      Version of Record online: 13 SEP 2005 | DOI: 10.1002/pola.20973

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      A tridentate ligand, 2,6-bis[1-(2,6-diisopropylphenylimino) ethyl] pyridine BPIEP, was effectively employed in controlled/“living” radical polymerization of MMA. Well-defined polymers with polydispersities Mw/Mn ≤ 1.23 are obtained using ethyl-2-bromoisobutyrate as initiator in the presence of CuIBr in toluene at 90°C. The apparent activation energy (ΔEapp) of the polymerization was found to be 58.29 KJ mol and enthalpy of equilibrium (ΔH0eq) to 28.8 KJ mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as in solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiment.

    2. Synthesis of electroluminescent copoly(aryl ether)s containing alternate 1,4-distyrylbenzene derivatives and aromatic 1,3,4-oxadiazole or 3,3″-terphenyldicarbonitrile segments (pages 5009–5022)

      Bar-Yuan Hsieh, Kun-Ming Yeh and Yun Chen

      Version of Record online: 13 SEP 2005 | DOI: 10.1002/pola.20975

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      New copoly(aryl ether)s (P1–P3) containing alternate distyrylbenzene derivatives and aromatic 1,3,4-oxadiazole or 3,3″-terphenyldicarbonitrile segments have been prepared and characterized. They are basically amorphous materials with 5% weight-loss temperature above 410 °C. Their emissions are exclusively dominated by 1,4-distyrylbenzene segments via excitation energy transfer from electron-transporting 1,3,4-oxadiazole or 3,3″-terphenyldicarbonitrile chromophores. Electrochemical results confirm that oxidation and reduction start from the emitting 1,4-distyrylbenzene and electron-transporting segments, respectively. The turn-on field and maximum luminance of a two-layer EL device (ITO/PEDOT/P1/Al) are 4 × 105 V/cm and 225 cd/m2, respectively, and the emission peak is at about 500 nm.

    3. Preparation and characterization of redox cellulose Langmuir–Blodgett films containing a ferrocene derivative (pages 5023–5031)

      Shinsuke Ifuku, Yoshinobu Tsujii, Hiroshi Kamitakahara, Toshiyuki Takano and Fumiaki Nakatsubo

      Version of Record online: 14 SEP 2005 | DOI: 10.1002/pola.20980

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      6-O-(4-stearyloxytrityl)cellulose having ferrocene moiety, one of the redox species, was prepared and formed a homogeneous monolayer. The monolayer was transferred successively as a X-type LB film. Successful deposition was confirmed by UV absorption spectra. FTIR spectra and X-ray diffraction measurements indicated that the thickness of the monolayer in the LB film was 1.99 nm, hydrocarbon chains are oriented considerably perpendicular to the surface of the plate with a trans-zigzag conformation, and the C[DOUBLE BOND]O group of ferrocene moiety was oriented perpendicularly to the substrate. The rate of interfacial electron-transfer process between the ferrocene moiety and the electrode surface was fast enough.

    4. Preparation and polymerization of a water-soluble, nonbonding crosslinking agent for a mechanically crosslinked hydrogel (pages 5032–5040)

      Masataka Kubo, Toyohiro Matsuura, Hiromi Morimoto, Takahiro Uno and Takahito Itoh

      Version of Record online: 14 SEP 2005 | DOI: 10.1002/pola.20982

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      A novel water-soluble cyclic macromonomer based on a cyclic potassium polyacrylate was prepared. The radical polymerization of acrylamide in the presence of the cyclic macromonomer was carried out to obtain a mechanically crosslinked polyacrylamide. The terpolymerization of acrylamide, sodium acrylate, and the cyclic macromonomer gave a mechanically crosslinked polyelectrolyte with high swellability. The mechanically crosslinked polyelectrolyte exhibited large volume shrinkage in a water solution of Cu(II) salt.

    5. Consideration of the mechanism of styrene/ethylene copolymerization with half-titanocene catalysts (pages 5041–5048)

      Kiyohiko Yokota, Tsuneaki Kohsaka, Kazuhiko Ito and Nobuhide Ishihara

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/pola.20948

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      From the whole polymer obtained with a cyclopentadienyltitanium trichloride/methylaluminoxane catalyst system, poly(styrene-block-ethylene) contained syndiotactic styrene–styrene sequences was separated with the temperature rising elution fractionation method, and the structure was specified by 13C NMR. The polymer obtained from the trivalent titanium catalyst, which was thought to be the active species of syndiotactic polystyrene, included both a styrene–styrene sequence and a styrene–ethylene–ethylene–styrene sequence. However, neither the styrene–ethylene–styrene sequence nor the long chain of polyethylene was included.

    6. Synthesis and characterization of amphiphilic triblock copolymers by iron-mediated atom transfer radical polymerization (pages 5049–5061)

      Khalid Ibrahim, Paul Starck, Barbro Löfgren and Jukka Seppälä

      Version of Record online: 14 SEP 2005 | DOI: 10.1002/pola.20958

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      Atom transfer radical polymerization was performed to synthesize water-soluble/dispersible A–B–A amphiphilic triblock copolymers, with methyl methacrylate as the A block and poly(ethylene oxide) (PEO) as the B block, with iron(II) chloride tetrahydrate in the presence of triphenylphosphine ligand (FeCl2·4H2O/PPh3) as the catalyst. At low monomer-to-macroinitiator molar ratios, the glass transitions of both PEO and poly(methyl methacrylate) (PMMA) blocks were detected by differential scanning calorimetry, which confirmed that phase separation had taken place. The use of PEO with a higher chain length in the polymerizations also led to phase separation of the blocks.

    7. High electroluminescent properties of conjugated copolymers from poly[9,9-dioctylfluorenyl-2,7-vinylene]-co-(2-(3-dimethyldodecylsilylphenyl)-1,4-phenylene vinylene)] for light-emitting diode applications (pages 5062–5071)

      Sung-Ho Jin, Hwan-Hee Jung, Chan-Koo Hwang, Dae-Sung Koo, Won Suk Shin, Yeong-Inn Kim, Jae Wook Lee and Yeong-Soon Gal

      Version of Record online: 14 SEP 2005 | DOI: 10.1002/pola.20994

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      A new series of copolymers with high brightness and luminance efficiency were synthesized using the Gilch polymerization method, and their electro-optical properties were investigated. Thin films of poly(FV), poly(m-SiPhPV), and poly(FV-co-m-SiPhPV) were found to exhibit photoluminescence quantum yields between 21% and 42%. Light-emitting diodes were fabricated in ITO/PEDOT/light-emitting polymer/cathode configurations using either double layer (LiF/Al) or triple layer (Alq3/LiF/Al) cathode structures. The turn-on voltages of the PLEDs were in the range of 4.5–6.0 V, with maximum brightness and luminance efficiency up to 9691 cd/m2 at 16 V and 3.27 cd/A at 13 V, respectively.

    8. The synthesis of novel aliphatic bis(acenaphthelene) reactive monomers (pages 5072–5082)

      Tim J. Wooster, Simmi Abrol, Jeffrey M. Hey and Douglas R. MacFarlane

      Version of Record online: 14 SEP 2005 | DOI: 10.1002/pola.20974

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      A new series of bis(acenaphthanelene) reactive monomers was synthesized using aliphatic bridging groups. These were readily produced with long aliphic diacid chlorides. The procedure for reactive group introduction was also refined, from dehydrobromination to debromination. This lead to the production of pure monomer, rather than a mixture of monomer and oligomer as previous routes did. The refinement leads to the introduction of a processing window that enabled melt casting of polymeric samples. The resultant polymerised products were found to have high thermal stability and are potential alternatives for electronic encapsulation applications.

    9. Optical and electrochemical properties of copoly(aryl ether)s consisting of alternate 2,5-distyrylbenzene and electron-transporting oxadiazole or triazole derivatives (pages 5083–5096)

      Shinn-Horng Chen and Yun Chen

      Version of Record online: 19 SEP 2005 | DOI: 10.1002/pola.20866

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      Copoly(aryl ether) P1 with alternate electron- and hole-transporting segments was synthesized via nucleophilic substitution polymerization. Optical and electrochemical properties of P1P3 and other copoly(aryl ether)s, which contain the same hole-transporting 2,5-distyrylbenzene segments, have been investigated. Photoluminescence of these copoly(aryl ether)s are all attributed to hole-transporting segments (energy acceptors) via energy transfer. However, protonation of donors diminishes the energy transfer significantly. The HOMO levels of P1P3 are −5.12, −5.15, and −5.18 eV; and the LUMO levels are −2.93, −3.39, and −3.49 eV, respectively.

    10. Synthesis of novel core-crosslinked graft copolymers from crosslinked poly(mercapto-thiourethane) (pages 5097–5102)

      Bungo Ochiai and Takeshi Endo

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/pola.20937

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      Graft copolymers with high grafting efficiency (>1800%) were prepared by radical copolymerization of styrene and MMA in the presence of crosslinked poly(mercapto-thiourethane).

    11. Syntheses of graft and star copolymers possessing polyolefin branches by using polyolefin macromonomer (pages 5103–5118)

      Hideyuki Kaneko, Shin-ichi Kojoh, Nobuo Kawahara, Shingo Matsuo, Tomoaki Matsugi and Norio Kashiwa

      Version of Record online: 19 SEP 2005 | DOI: 10.1002/pola.20963

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      New graft and star copolymers having poly(methacrylate) backbone and ethylene–propylene random copolymer (EPR) branches were synthesized by radical polymerization of EPR macromonomer with methyl methacrylate (MMA), using monofunctional and tetrafunctional initiators. The obtained copolymers demonstrated well-dispersed morphologies between PMMA and EPR, and their characteristics as a compatibilizer in blending EPR and PMMA.

    12. Novel siloxane-carrying dithiol derived from 5-membered cyclic dithiocarbonate and its curing reactions for coating application (pages 5119–5126)

      Kazuya Uenishi, Atsushi Sudo and Takeshi Endo

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/pola.21005

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      DTC-Si was found to be a useful reagent to convert amines into the corresponding siloxane-functionalized thiols. Based on this reaction, an amine-terminated polyether was successfully transformed to the corresponding thiol-terminated one, functionalized with siloxane group. The thiol thus formed at the chain ends reacted with epoxide, and the siloxane underwent not only condensation reaction, but also forms covalent bond with silicate surface to immobilize the related materials onto it. These reactivity features of the present thiol-siloxane hybrid molecules make them highly attractive as curable materials, and the facile and straightforward method for the transformation would promote us to design tailor-made coating materials having appropriate properties for various applications.

    13. Preparation and characterization of novel hyperbranched poly(amido amine)s from Michael addition polymerizations of trifunctional amines with diacrylamides (pages 5127–5137)

      Ding Wang, Ye Liu, Chun-Yan Hong and Cai-Yuan Pan

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/pola.21004

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      Michael addition polymerizations of trifunctional amines with twofold molar diacrylamide yields novel hyperbranched poly(amido amine)s containing tertiary amines in the backbones and acryl as terminal groups. Based on the reactivity order of three types of amines, 2° amine (original) > 1° amine ≫ 2° amine (formed), the AB2 monomer with two acryl groups and one 2° amine is firstly formed, and subsequent polymerization of this AB2 monomer forms hyperbranched polymer.

    14. Living cationic polymerization of azobenzene-containing vinyl ether and its photoresponsive behavior (pages 5138–5146)

      Tomohide Yoshida, Shokyoku Kanaoka and Sadahito Aoshima

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/pola.20981

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      The living cationic polymerization of 4-[2-(vinyloxy)ethoxy]azobenzene (AzoVE) was achieved with various Lewis acids in the presence of an ester as an added base. When Et1.5AlCl1.5 was used as a catalyst, the living polymerization system was controllable by UV irradiation as a result of cis and trans isomerization of the azobenzene side groups. Furthermore, an initiating system consisting of SnCl4 and EtAlCl2 realized fast living polymerization of AzoVE. A solution of poly(4-[2-(vinyloxy)ethoxy]azobenzene) in diethyl ether/hexane demonstrated photoinduced phase-separation behavior with sensitive and perfect reversibility upon alternating irradiation with UV or visible light.

    15. Poly(p-phenylenevinylene) presenting pendent pentaphenylene dendron groups for light-emitting diodes (pages 5147–5155)

      Ya-Hsien Tseng, Fang-Iy Wu, Ping-I Shih and Ching-Fong Shu

      Version of Record online: 20 SEP 2005 | DOI: 10.1002/pola.20992

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      We have synthesized a dendronized polymer, PPV-PP, that consists of a conjugated poly(p-phenylenevinylene) backbone on which are appended pentaphenylene dendritic wedges. As a result of incorporating the dendritic pentaphenylene pendent groups, which reduce the strength of interchain interactions and suppress the formation of excimers, PPV-PP is soluble in common organic solvents and exhibits high photoluminescence efficiency in the solid state. Polymer light-emitting diodes that we fabricated in the configuration ITO/PEDOT/PPV-PP/Mg:Ag/Ag exhibited a maximum luminance efficiency of 1.93 cd/A.

    16. Synthesis and characterization of thermoresponsive amphiphilic block copolymers incorporating a poly(ethylene oxide-stat-propylene oxide) block (pages 5156–5167)

      Katherine B. Aubrecht and Robert B. Grubbs

      Version of Record online: 22 SEP 2005 | DOI: 10.1002/pola.21007

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      Biocompatible amphiphilic BuO-(PEO-stat-PPO)-block-PLA-OH diblock and MeO-PEO-(PEO-stat-PPO)-block-PLA-OH triblock copolymers incorporating thermoresponsive (PEO-stat-PPO) blocks were prepared by ring-opening polymerization of lactide. Aqueous solutions of these block copolymers display cloud points. Preliminary characterization of the polymeric micelles points to significant changes in the size of the micellar aggregates as function of temperature. [Color figure can be viewed in the online issue, which is available at]

    17. Synthesis and helical conformation of poly(N-propargylamides) carrying L-aspartic acid in the side chain (pages 5168–5176)

      Haichao Zhao, Fumio Sanda and Toshio Masuda

      Version of Record online: 20 SEP 2005 | DOI: 10.1002/pola.21001

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      L-Aspartic acid-containing polyacetylenes [poly(1) and poly (2)] with moderate molecular weights were synthesized. The helicity of poly(1) could be tuned by temperature and solvents. Poly(2) transformed the structure from helix into random coil in toluene upon heating. Poly(2) underwent solvent-driven helix-random coil and helix–helix transitions in a mixture of CHCl3/MeOH and CHCl3/toluene.

    18. Surface-modified hydroxyapatite linked by L-lactic acid oligomer in the absence of catalyst (pages 5177–5185)

      Xueyu Qiu, Li Chen, Junli Hu, Jingru Sun, Zhongkui Hong, Aixue Liu, Xuesi Chen and Xiabin Jing

      Version of Record online: 20 SEP 2005 | DOI: 10.1002/pola.21006

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      L-Lactic acid oligomer with carboxyl was grafted on the surface of hydroxyapatite nanoparticles in the absence of any catalyst. The grafting of L-lactic acid oligomer improved the compatibility between the hydroxyapatite filler and the PLLA matrix; thus the modified hydroxyapatite/PLLA composites exhibited better mechanical properties and thermal stability than pure HA/PLLA composites did.

    19. Organosoluble star polymers from a cyclodextrin core (pages 5186–5194)

      Khaled Karaky, Stéphanie Reynaud, Laurent Billon, Jeanne François and Yamama Chreim

      Version of Record online: 20 SEP 2005 | DOI: 10.1002/pola.21012

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      Well-defined star polymers were synthesized with a combination of the core-first method and atom transfer radical polymerization. The star polymer included a cyclodextrin core and organosoluble arms. The first step of the process was the optimization of the experimental conditions of the acetylation of α-cyclodextrin and β-cyclodextrin. Well-defined modified cyclodextrins were characterized. The ability of this kind of modified cyclodextrin to initiate atom transfer radical polymerization was checked in a second step. The polymerization conditions were established to produce well-defined architectures. Star polymers were obtained with predictable molecular weights. These new star polymers are promising precursors to innovative polyelectrolytes able to clean contaminated water.

    20. Spontaneous reactions of electron-accepting substituted quinodimethane with substituted styrenes: Inductive and steric effects on the formation of a zwitterionic intermediate (pages 5195–5206)

      Yukihiro Mitsuda, Takahiro Uno, Masataka Kubo and Takahito Itoh

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.21014

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      The spontaneous reaction mechanism of electron-accepting substituted quinodimethane with substituted styrenes was investigated. The inductive and steric effects of substituents in the substituted styrenes on the formation of zwitterionic intermediates were discussed.

    21. Atom transfer radical polymerization of methyl methacrylate catalyzed by cobalt catalyst system (pages 5207–5216)

      Zhong Hui Li, Yong Ming Zhang, Min Zhao Xue, Lei Zhou and Yan Gang Liu

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.20835

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      A new catalyst system, CoCl2/tris(2-(dimethyl amino) ethyl)amine (Me6TREN), was used to catalyze the polymerization of MMA successfully through atom transfer radical polymerization mechanism. The control over the cobalt-mediated polymerization was significantly improved when a small amount of hybrid deactivator (FeBr3/Me6TREN or CuBr2/Me6TREN) was added affording polymer with a high initiation efficiency and a narrow molecular weight distribution (Mw/Mn = 1.15–1.46).

    22. Curcumin: A naturally occurring long-wavelength photosensitizer for diaryliodonium salts (pages 5217–5231)

      James V. Crivello and Umut Bulut

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.21017

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      Curcumin, a naturally occurring, intensely orange-yellow dye extracted from the spice turmeric, is an efficient photosensitizer for onium salt photoinitiators at wavelengths ranging from 340 to 535 nm. With curcumin as a photosensitizer, it is possible to carry out the cationic photopolymerization of a wide variety of epoxide, oxetane, and vinyl monomers with long-wavelength UV and visible light.

    23. Controlled radical polymerization of styrene and methyl acrylate in the presence of reversible addition–fragmentation chain transfer agents, phenylethyl phenyl dithioacetate and phenyldithioacetic acid (pages 5232–5245)

      Yong-Keng Goh, Michael R. Whittaker and Michael J. Monteiro

      Version of Record online: 20 SEP 2005 | DOI: 10.1002/pola.21020

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      Homopolymerizations of styrene or methyl acrylate with phenyldithioacetic acid (PDA) went by different mechanistic pathways. Styrene favors addition of styrene to PDA via a Markovnikov type addition to form a reactive RAFT agent and methyl acrylate by degradative chain transfer. A unique feature of this work was that PDA could be used to form a RAFT agent in situ by heating a mixture of styrene and PDA for 24 h at 70 °C, and then polymerizing in the presence of AIBN to give a linear increase in Mn and low values of PDI (<1.14).

    24. Some novel accelerating agents for nitroxide-mediated living free-radical polymerization (pages 5246–5256)

      Huang Jianying, Lin Jian, Lin Minghua, Lin Qiang, Dai Lizong and Zou Yousi

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.20840

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      The rate of polymerization of nitroxide-mediated free-radical polymerization processes for styrene (St) and copolymerization can be dramatically increased by the addition of trifluoroacetic acid anhydride, acetylacetone, acetoacetic ester, diethyl malonate, and malononitrile (MN). MN has the greatest accelerating effect. Adding MN at an MN/2,2,6,6-tetramethylpiperidine-oxyl (TEMPO) molar ratio of 4.0 results in a nearly 20 times higher rate of polymerization of St, and adding MN at an MN/TEMPO molar ratio of 2.5 results in a nearly 15 times higher rate of copolymerization of St and methyl methacrylate. The polymerization of St proceeds in a living fashion. The polymerization rate of St is so quick that the conversion reaches 70% within 1 h at 125 °C when the molar ratio of MN to TEMPO is 4:1. Moreover, the reaction temperature can be reduced to 110 °C. A possible explanation for this effect is that the formation of hydrogen bonds between the MN and TEMPO moiety weakens the C[BOND]ON bond at the end of the polymer chain.

    25. Oligoethylene-end-capped polylactides (pages 5257–5266)

      Nilmini K. Abayasinghe, Sibylle Glaser, K. Prasanna, U. Perera and Dennis W. Smith Jr

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.20889

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      A series of copolymers were synthesized via the ring-opening polymerization of lactide with hydroxyl-terminated oligoethylene macroinitiators. The oligoethylene-end-capped polylactides exhibited number-average molecular weights of approximately 40,000 (weight-average molecular weight/number-average molecular weight = 1.7) according to gel permeation chromatography, and the differential scanning calorimetry analysis showed that they were highly crystalline in comparison with the similarly formed homopolymer of L-lactide. The copolymer structure was characterized by Fourier transform infrared, NMR, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis. These highly crystalline polylactide derivatives could be used as potential compatibilizers in polylactide–polyolefin blends or as nucleating agents for poly(L-lactide) or other polyesters.

    26. High performance benzoxazine monomers and polymers containing furan groups (pages 5267–5282)

      Ying-Ling Liu and Ching-I Chou

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.21023

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      Benzoxazines containing furan groups and their corresponding polymers were synthesized and characterized. Good processing properties, such as organo-solubility, low melting temperatures, and wide processing windows, were observed with the benzoxazine monomers. The polybenzoxazines exhibited superior thermal and mechanical properties, self-extinguishing behavior, and low dielectric constants.

    27. N-chloro amides, lactams, carbamates, and imides. New classes of initiators for the metal-catalyzed living radical polymerization of methacrylates (pages 5283–5299)

      Virgil Percec and Cristian Grigoras

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.21060

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      Aliphatic, aromatic, and aliphatic aromatic N-chloro amides, N-chloro lactams, N-Chloro carbamates, and N-Chloro imides represent new classes of initiators for metal-catalyzed living radical polymerization of methyl methacrylates.

    28. Polyisophthalamides with heteroaromatic pendent rings: Synthesis, physical properties, and water uptake (pages 5300–5311)

      Juan J. Ferreiro, Jose G. de la Campa, Angel E. Lozano and Javier de Abajo

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.21000

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      A set of novel aromatic polyamides containing pyridine pendent groups was prepared from aromatic diamines and new monomers that are 5-substituted derivatives of isophthalic acid bearing nicotinamide, isonicotinamide, or picolinamide groups, by the phosphorylation method of polycondensation. All of the polymers were soluble in polar aprotic solvents and gave films of good mechanical properties. Glass transition temperatures were higher than that of the reference polymer, poly(m-phenyleneisophthalamide) (IP-MPD), while the thermal resistance, defined by the initial decomposition temperature observed by thermogravimetry, was lower by 30–70 °C than that of IP-MPD. The presence of a pendent pyridine group and an additional amide side group per repeat unit made the polymers essentially amorphous and greatly improved their abilities to absorb water in comparison with nonsubstituted polyamides.

    29. Synthesis of fluorinated oligomers for supercritical carbon dioxide applications (pages 5312–5322)

      N. Bilgin, C. Baysal and Y. Z. Menceloglu

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.21015

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      Syntheses of various fluorine-based surfactants for scCO2 media-based applications were achieved by the radical polymerization of mainly acrylate-based monomers. A difunctional fluorinated initiator was synthesized from 4,4′-azobis-4-cyanovaleric acid and a fluorinated alcohol. It was utilized for the polymerization reactions carried out to obtain triblock co-oligomer consisting of fluorinated side blocks and a hydrocarbon intermediate block. It was experimentally shown that solubility efficiency is affected by specific interactions between CO2 and the oligomers, which are determined by the nature and the size of the inner block, and by the relative chain length of the fluorinated side blocks.

  3. Rapid Communications

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      Lewis acid-mediated double ring-opening reaction of an oligo(spiro-orthocarbonate): A novel class of expanding material (pages 5323–5327)

      Tetsuo Hino and Takeshi Endo

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.20966

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      As a novel approach for development of a new class of expanding material, we examined Lewis acid-mediated double ring-opening reactions of a highly rigid and rodlike prepolymer consisting of labile, volume-expanding bicyclic moieties, oligo (spiroorthocarbonate) (o-SOC). As a result, the treatment with large amount of BF3·OEt2 at 100 °C for 24 h in toluene gave the corresponding networked product showing unexpected drastic volume expansion (∼30%). In addition, the 10% weight loss decomposition temperature and the glass transition temperature were higher than those of o-SOC.

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      Regio- and stereoselective synthesis of poly(arylenevinylene phosphine oxide)s by the metal-catalyzed addition polymerization of bisphosphoroyl compounds with diynes (pages 5328–5336)

      Li-Biao Han, Zuoxin Huang, Shigemoto Matsuyama, Yutaka Ono and Chang-Qiu Zhao

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.21002

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      The addition of bisphosphoroyl compounds to diynes took place efficiently in the presence of a trace amount of transition-metal complexes to produce novel poly(arylenevinylene phosphine oxide)s in good yields with molecular weights in a range of 1 × 104 to 1 × 105. Both the stereoselectivity and regioselectivity of the addition are fully controllable to give either the corresponding structurally defined poly(trans-alkenylene)s via Markovnikov additions or the corresponding poly(gem-vinylene)s via anti-Markovnikov additions of the P(O)[BOND]H bonds to the carbon–carbon triple bonds.

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      Photo-responsive copolymers with azobenzene side groups synthesized by living cationic polymerization: Efficient amplification of photosensitivity in aqueous photo-switching system (pages 5337–5342)

      Tomohide Yoshida, Shokyoku Kanaoka and Sadahito Aoshima

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.21009

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      Random and block copolymers of 4-[2-(vinyloxy)ethoxy]azobenzene (AzoVE) and various vinyl ethers (exhibiting LCST-type phase separation) were prepared by living cationic polymerization using 1-(isobutoxy)ethyl acetate/Et1.5 AlCl1.5 in the presence of ethyl acetate at 0 °C. With random copolymers having thermally-responsive and azobenzene units, the phase separation occurs at a higher temperature under UV irradiation compared with that under visible light. This shift made it possible to control the solubility of the polymer by irradiating UV or visible light. Irradiation of a 20 wt % aqueous solution of (AzoVE2-r-EOEOVE200)-b-MOVE400 with visible light caused rapid gelation to give a transparent gel at 42.6 °C. Under subsequent irradiation with UV light, the gel returned to a fluid state with the same viscosity of the initial solution.

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      Synthesis of poly(acrylamide-co-divinylbenzene) microspheres by precipitation polymerization (pages 5343–5346)

      Jeong Min Jin, Sunhye Yang, Sang Eun Shim and Soonja Choe

      Version of Record online: 23 SEP 2005 | DOI: 10.1002/pola.20985

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      Highly crosslinked poly(acrylamide-co-divinylbenzene) microspheres have been prepared by precipitation polymerization in the presence of an acetonitrile medium. The divinylbenzene concentration plays a pivotal role in not only the formation of individually stable microspheres but also the polymerization characteristics, including the final size, uniformity of the particle size, yield of the polymerization, and thermal properties.