Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 20

15 October 2005

Volume 43, Issue 20

Pages 4675–4979

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      Ionic liquids in the synthesis and modification of polymers (pages 4675–4683)

      Przemysław Kubisa

      Article first published online: 1 SEP 2005 | DOI: 10.1002/pola.20971

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      Ionic liquids are organic salts liquid at ambient temperatures, preferably at room temperature. In recent years, ionic liquids have attracted the attention of polymer chemists. Although the research on using ionic liquids in polymer systems is still in its infancy, several interesting possibilities have already emerged. Ionic liquids are used as solvents for polymerization processes. Ionic liquids, as electrolytes, have also attracted the attention of researchers in the field of electrochemical polymerization. The blending of ionic liquids with polymers may lead to the development of new materials. In this article, the new developments in these fields are briefly discussed.

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    1. Cross-linking emulsion copolymerization of butyl acrylate with diallyl maleate (pages 4684–4694)

      Ludivine Bouvier-Fontes, Rosangela Pirri, José M. Asua and Jose R. Leiza

      Article first published online: 2 SEP 2005 | DOI: 10.1002/pola.20930

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      The emulsion copolymerization of butyl acrylate (BA) with a trifunctional cross-linker, the diallyl maleate (DAM), was investigated. The effect of the monomer feeding time and the amount of cross-linker on the microstructural properties (branching, cross-linking, gel formation, and sol MWD) of the seeded semicontinuous emulsion copolymerization of BA with DAM was investigated. In addition, the effect of process type, batch versus semibatch, was also considered and important differences in the level of quaternary carbons, cross-linking, and gel content were found.

    2. ATRP of butyl acrylates from functionalized carbon black surfaces (pages 4695–4709)

      Tianqi Liu, Rosa Casado-Portilla, James Belmont and Krzysztof Matyjaszewski

      Article first published online: 31 AUG 2005 | DOI: 10.1002/pola.20931

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      Functionalization of carbon black surface with atom transfer radical polymerization (ATRP) initiating sites and subsequent ATRP of n-butyl acrylate (n-BA) and t-butyl acrylate (t-BA) from the particle surface in anisole was studied. The initiator density on the surface was varied and the effect of initiator density on the polymers grafted on the surface was illustrated. Water-dispersible carbon black was achieved by block copolymerization of n-BA and t-BA followed by cleavage of the t-butyl groups.

    3. Synthesis of gold nanocomposite via chemisorption of gold nanoparticles with poly(p-methylstyrene) containing multiple bonding groups on the chain side (pages 4710–4720)

      Hsuan-Ming Huang, Ching-Yu Chang, I-Chun Liu, Hung-Chieh Tsai, Mei-Kuan Lai and Raymond Chien-Chao Tsiang

      Article first published online: 31 AUG 2005 | DOI: 10.1002/pola.20940

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      Styrenic nanocomposite containing gold nanoparticles (AuNPs) has been synthesized by anchoring polymer molecules containing multiple functional groups onto the gold surface. p-Methylstyrene was first anionically polymerized and the resulting polymer was chlorinated with sodium hypochlorite in the presence of a phase-transfer catalyst. The chlorinated poly(p-methylstyrene) was next reacted with methylthiomethyllithium, which had been prepared via a metalation reaction of dimethyl sulfide with n-butyllithium, to form a styrenic polymer containing thioether groups on the sides of the molecule. These thioether groups on the chain sides afforded more chemisorption sites per molecule to AuNPs. The nanocomposite was analyzed with NMR, TEM, UV-VIS, TGA, and XPS. [A color version of the adjacent figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    4. Supramolecular inclusion complexes of star-shaped poly(ε-caprolactone) with α-cyclodextrin (pages 4721–4730)

      Lu Wang, Jing-Liang Wang and Chang-Ming Dong

      Article first published online: 1 SEP 2005 | DOI: 10.1002/pola.20999

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      Both star-shaped poly(ε-caprolactone) having 4 arms (4sPCL) and 6 arms (6sPCL) and linear PCL having 1 arm (LPCL) and 2 arms (2LPCL) were synthesized and then investigated for inclusion complexation with α-cyclodextrin (α-CD). The stoichiometry (CL:CD, mol:mol) of all ICs increased with the increasing branch arm of PCL polymers, and it was in the order of α-CD-6sPCL1 ICs > α-CD-4sPCL ICs > α-CD-2LPCL ICs > α-CD-LPCL ICs. All analyses indicated that the branch arms of star-shaped PCL polymers were included into the hydrophobic α-CD cavities and their original crystalline properties were completely suppressed. Moreover, the ICs of star-shaped PCL with α-CD had a channel-type crystalline structure similar to that formed between the linear PCL and α-CD. Furthermore, the thermal stability of the free PCL polymers probably controlled that of the guest polymers included in the ICs.

    5. Synthesis of main-chain hydrogen-bonded supramolecular liquid crystalline complexes: The effects of spacer on thermal behavior of mesophase (pages 4731–4743)

      Cher Ling Toh, Jianwei Xu, Xuehong Lu and Chaobin He

      Article first published online: 31 AUG 2005 | DOI: 10.1002/pola.20969

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      Two series of difunctional stilbazole-containing proton acceptors were synthesized. Hydrogen-bonded polymeric and trimeric complexes were prepared, and their thermotropic liquid crystallinity was examined. The study of effects of spacers and terminal groups on the thermal behaviors of the complexes revealed that transition temperatures were dominated by a component with a more flexible spacer. The terminal group played diverse roles in affecting the transition temperatures of trimeric complexes, depending upon the flexibility of the spacer in the proton acceptors. [A color version of the adjacent figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    6. Tacticity of poly-α-olefins from poly-1-hexene to poly-1-octadecene (pages 4744–4753)

      Griselda Barrera Galland, Luciano Forgiarini Da Silva and Adriana Nicolini

      Article first published online: 2 SEP 2005 | DOI: 10.1002/pola.20989

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      Isotactic and syndiotactic poly-α-olefins, from 1-hexene to 1-octadecene were obtained using the catalytic systems rac-Et[Ind]2ZrCl2/MAO and Me2C[Cp(9-Flu)]ZrCl2/MAO. A systematic study of the influence of the α-olefin size, the catalyst stereospecificity and the reactional temperature was done on the catalytic activity and the tacticity. Catalysts giving atactic polyolefins were also used to study all the possible 13C-NMR pentades.

    7. Hyperbranched fluorocopolymers by atom transfer radical self-condensing vinyl copolymerization (pages 4754–4770)

      Chong Cheng, Karen L. Wooley and Ezat Khoshdel

      Article first published online: 2 SEP 2005 | DOI: 10.1002/pola.20987

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      Hyperbranched fluorocopolymers with controlled fluorine contents, adjustable degrees of branching, various reactive sites, and excellent solubility were synthesized by the atom transfer radical self-condensing vinyl copolymerization of an inimer, either p-chloromethylstyrene or p-bromomethylstyrene, with pentafluorostyrene.

    8. Synthesis and characterization of novel biodegradable block copolymer poly(ethylene glycol)-block-poly(L-lactide-co-2-methyl-2-carboxyl-propylene carbonate) (pages 4771–4780)

      Hui-Li Guan, Zhi-Gang Xie, Pei-Biao Zhang, Xin Wang, Xue-Si Chen, Xian-Hong Wang and Xia-Bin Jing

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20942

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      An amphiphilic block copolymer, PEG-b-P(LA-co-MBC), was synthesized by the ROP of LA and MBC in the presence of PEG and ZnEt2. Its catalytic hydrogenation was performed to obtain the corresponding copolymer PEG-b-P(LA-co-MCC) with pendant carboxyl groups. DSC analysis indicated that Tg of PEG-b-P(LA-co-MBC) decreased with increasing MBC content, and Tg of PEG-b-P(LA-co-MCC) was higher than that of the corresponding PEG-b-P(LA-co-MBC). The in vitro degradation rate of PEG-b-P(LA-co-MCC) in the presence of proteinase K was faster than that of PEG-b-P(LA-co-MBC), and the cytotoxicity of PEG-b-P(LA-co-MCC) to chondrocytes was lower than that of PLA.

    9. Cyclic poly(pyridine ether)s by the polycondensation of 2,6-difluoropyridine with various diphenols (pages 4781–4789)

      Hans R. Kricheldorf, Mazen Garaleh and Gert Schwarz

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20944

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      2,6-Difluoropyridine was polycondensed with various silylated diphenols in N-methylpyrrolidone, and the reactions conditions were optimized for high molar masses. The chain growth was limited by efficient cyclization. The influence of the diphenol structure on the cyclization tendency was studied.

    10. New developments in the synthesis and characterization of phosphate esters of linear (per)fluoropolyether monofunctional and difunctional macromonomers (pages 4790–4804)

      Antonio Russo, Claudio Tonelli and Emma Barchiesi

      Article first published online: 2 SEP 2005 | DOI: 10.1002/pola.20945

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      The synthesis and NMR characterization of (per)fluoropolyether phosphate esters, prepared by the reaction of P2O5 with the corresponding monofunctional and difunctional alcohols, have been investigated. The addition of a modulated amount of water to the starting fluorinated alcohol allows the fine-tuning of the ratio between the monoalkylester and dialkylester in the final products.

    11. Preparation by controlled radical polymerization and self-assembly via base-recognition of synthetic polymers bearing complementary nucleobases (pages 4805–4818)

      Jean-François Lutz, Andreas F. Thünemann and Rainer Nehring

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20976

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      A new series of copolymers based on styrene derivatives bearing nucleobases (adenine or thymine) and dodecyl methacrylate was studied. These copolymers could be prepared in high yield via both conventional radical polymerization and atom transfer radical polymerization. Moreover UV spectroscopy studies indicated that complementary copolymers bearing adenine and thymine functionalities self-assemble in dilute chloroform or dioxane solutions due to base pairing. Nevertheless, at higher concentrations in chloroform, both dynamic light scattering and optical microscopy indicated that P(VBT-co-DMA), P(VBA-co-DMA), or P(VBT-co-DMA)/P(VBA-co-DMA) mixtures spontaneously self-assemble into micron-size spherical aggregates.

    12. Hydrophilic–hydrophobic AB diblock copolymers containing poly(trimethylene carbonate) and poly(ethylene oxide) blocks (pages 4819–4827)

      Yakai Feng and Shifeng Zhang

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20929

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      AB-type diblock copolymers with poly(trimethylene carbonate) [poly(TMC)] as a hydrophobic block and poly(ethylene oxide) (PEO) as a hydrophilic block were synthesized via the ring-opening polymerization of trimethylene carbonate in the presence of PEO with stannous octoate [Sn(oct)2]. The thermal properties were investigated with differential scanning calorimetry. The surface and hydrophilicity properties were studied with contact-angles and atomic force microscopy. Compared with poly(TMC), the diblock copolymers had a higher Young's modulus and lower elongation at break

    13. Synthesis of triblock copolymers based on two isomer acrylate monomers by atom transfer radical polymerization (pages 4828–4837)

      Alexandra Muñoz-Bonilla, María L. Cerrada and Marta Fernández-García

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20951

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      Two series of triblock copolymers with different molecular weights were synthesized with atom transfer radical polymerization. Difunctional macroinitiators of tert-butyl and iso-butyl acrylates with different lengths were used in the copolymerization with cyclohexyl methacrylate. Triblock copolymers with controlled molecular weights and narrow polydispersities were achieved. The determination of the glass-transition temperature indicated the tendency of these triblock copolymers to undergo phase segregation.

    14. Side-chain terpyridine polymers through atom transfer radical polymerization and their ruthenium complexes (pages 4838–4848)

      Nikos P. Tzanetos, Aikaterini K. Andreopoulou and Joannis K. Kallitsis

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20950

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      Atom transfer radical polymerization was used to prepare homopolymers having well-defined architectures and controllable molecular weights and molecular weight distributions and containing side-chain terpyridine ligands. Moreover, with the ruthenium(III)/ruthenium(II) complexation chemistry, a terpyridine/ruthenium(III) monocomplex was grafted onto each side 2,2′:6′,2″-terpyridine moiety of the initial polymers, and this resulted in highly soluble polymeric complexes.

    15. Influence of the chemical structure of dithiocarbamates with different N-groups on the reversible addition–fragmentation chain transfer polymerization of styrene (pages 4849–4856)

      Di Zhou, Xiulin Zhu, Jian Zhu and Haishu Yin

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20947

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      Polymerizations of styrene with azobisisobutyronitrile initiation or thermal initiation have been performed in the presence of dithiocarbamates with different N-groups. The results show that the structure of the N-group of dithiocarbamates has significant effects on the activity of dithiocarbamates for the polymerization of styrene, and the polymerization rate is markedly influenced by the conjugation structure of the N-group of the dithiocarbamate.

    16. Synthesis and characterization of biodegradable triblock copolymers based on bacterial poly[(R)-3-hydroxybutyrate] by atom transfer radical polymerization (pages 4857–4869)

      Xueqin Zhang, Hu Yang, Quanwei Liu, Yun Zheng, Hongfeng Xie, Zhiliu Wang and Rongshi Cheng

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20953

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      Biodegradable poly(tert-butyl acrylate)–poly[(R)-3-hydroxybutyrate]–poly(tert-butyl acrylate) (PtBA–PHB–PtBA) triblock copolymers based on bacterial poly[(R)-3-hydroxybutyrate] (PHB) were synthesized by atom transfer radical polymerization. The triblock copolymers underwent stepwise thermal degradation and had better thermal stability than their respective homopolymers, whereas a microphase-separation structure was formed only in the triblock copolymers with the longer PHB block. The biodegradability of the triblock copolymers increased with an increase in the PHB block content.

    17. Preparation of polyurethane dispersions by miniemulsion polymerization (pages 4870–4881)

      Chien-Yu Li, Wen-Yen Chiu and Trong-Ming Don

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20959

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      With a two-step miniemulsion polymerization, hydrophobic polyurethane (PU) dispersions were prepared with a cosurfactant, the costabilizer hexadecane (HD) in the oil phase, and sodium dodecyl sulfate (SDS) in the water phase. The first step involved the formation of NCO-terminated prepolymers between isophorone diisocyanate and poly(propylene glycol) oligomer in toluene. Next, PU dispersions were produced by a miniemulsion method in which an oil phase containing NCO-terminated prepolymers, HD, the chain extender 1,4-butanediol (BD), the crosslinking agent trimethylol propane (TMP), and the catalyst dibutyltin dilaurate was dispersed in the water phase containing SDS. The influence of experimental parameters, such as the ultrasonication time, concentrations of SDS and HD, and TMP/BD and NCO/OH equivalent ratios, on the sizes of the miniemulsion droplets and polymer particles, as well as the molecular weights and thermal properties of the PU polymer, was examined.

    18. Radical-mediated modification of polypropylene: Selective grafting via polyallyl coagents (pages 4882–4893)

      Saurav S. Sengupta, J. Scott Parent and J. Keith McLean

      Article first published online: 6 SEP 2005 | DOI: 10.1002/pola.20952

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      Selective graft modifications of polypropylene (PP) are demonstrated in which desirable functionality is introduced without the degradation that accompanies conventional radical-mediated processes. Several synthetic strategies are explored, each exploiting the reactivity of polyallyl compounds and their derivatives to crosslink PP to the extent required to offset polymer fragmentation. Model compounds are used to demonstrate the principal modes of allyl group activation.

    19. Accelerated iterative strategy for the divergent synthesis of dendritic macromolecules using a combination of living radical polymerization and an irreversible terminator multifunctional initiator (pages 4894–4906)

      Virgil Percec, Cristian Grigoras, Tushar K. Bera, Bogdan Barboiu and Philippe Bissel

      Article first published online: 7 SEP 2005 | DOI: 10.1002/pola.20864

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      Terminator multifunctional initiator (TERMINI) is a concept developed in our laboratory for the design and synthesis of novel macromolecular architectures from commercial monomers. This article reports an accelerated method based on the combination of the TERMINI concept and the metal-catalyzed living radical polymerization of methyl methacrylate (MMA) initiated from a bifunctional initiator, phenoxybenzene 4,4′-disulfonyl chloride (PDSC).

    20. Photoreactive main-chain liquid-crystalline polyesters: Synthesis, characterization, and photochemistry (pages 4907–4921)

      Rosa M. Tejedor, Luis Oriol, Milagros Piñol, José Luis Serrano, Veronika Strehmel, Burkhard Stiller and Joachim Stumpe

      Article first published online: 12 SEP 2005 | DOI: 10.1002/pola.20956

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      The synthesis and thermal characterization of liquid-crystalline polyesters containing photoreactive units in the main chain are described. A study of the photochemical properties of polymeric solutions and films has been carried out to explore the applications of these materials as optical aligning layers of liquid crystals. Because of the crosslinking of the polymer, the photoinduced anisotropy is stable at high temperatures, and the liquid-crystalline molecules are insoluble in the irradiated polymer.

    21. Poly(silarylene–siloxane)polyimides from allyl-terminated oligoimides and hydride-functional silarylene–siloxanes via hydrosilylation polymerization (pages 4922–4932)

      Craig L. Homrighausen, Brent J. Kennedy and Erick J. Schutte

      Article first published online: 9 SEP 2005 | DOI: 10.1002/pola.20962

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      Research was focused on new synthetic routes to low-temperature-curable poly(silarylene–siloxane)polyimides. The synthesis of oligoimide and silarylene–siloxane blocks was followed by hydrosilylation polymerization to produce crosslinked copolymers. The silarylene–siloxane and polyimide blocks were characterized by IR and 1H NMR spectroscopy and size exclusion chromatography. High-temperature resistance of the copolymers was evaluated through measurement of heat distortion temperatures (THD) via thermomechanical analysis and by the determination of the weight loss at elevated temperatures via thermogravimetric analysis. Hydrosilylation curing was conducted at 60 °C in the presence of chloroplatinic acid (H2PtCl6). The copolymers displayed both high-temperature resistance and low-temperature flexibility.

    22. Poly(N-phenylmaleimide-co-acrylic acid)–copper(II) and poly(N-phenylmaleimide-co-acrylic acid)–cobalt(II) complexes: Synthesis, characterization, and thermal behavior (pages 4933–4941)

      O. G. Marambio, G. del C. Pizarro, M. Jeria-Orell, M. Huerta, Claudio Olea-Azar and W. D. Habicher

      Article first published online: 9 SEP 2005 | DOI: 10.1002/pola.20955

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      The free radical copolymerization of N-phenylmaleimide (N-PhMI) with acrylic acid (AA) has been studied in the range from 25–75 mol % in the feed. The interactions of these copolymers with Cu(II) and Co(II) ions were investigated as a function of the pH and copolymer composition by the use of the ultrafiltration technique. Copolymers and polymer-metal complexes of divalent transition metal ions were characterized by elemental analysis, FT-IR, 1H NMR, ESR spectroscopies, and cyclic voltammetry. Thermal behavior was investigated by using differential scanning calorimetry (DSC) and thermogravimetry (TG).

    23. Effect of alkyl substituents structures and added ions on the phase transition of polymers and gels prepared from methyl 2-alkylamidoacrylates (pages 4942–4952)

      Takeshi Mori, Masafumi Hamada, Toru Kobayashi, Hirokazu Okamura, Keiji Minagawa, Seizo Masuda and Masami Tanaka

      Article first published online: 9 SEP 2005 | DOI: 10.1002/pola.20964

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      The effects of structure alteration of alkyl groups and addition of ions to solutions of new thermosensitive polymers series of poly(methyl 2-alkylamidoacrylate)s were investigated. Water solubility, transition heat, and continuity of volume change of the polymers could be explained by difference of the hydration structures around their hydrophobic groups. The inorganic (I and SCN) and organic ions (nPr4N+ and nBu4N+), which showed the salting-in effect, were indicated to directly interact with PMPA chains. These ions reduced cooperativity of the phase transition of the PMPA solutions.

    24. Ideal tetrafunctional amphiphilic PEG/PDMS conetworks by a dual-purpose extender/crosslinker. I. Synthesis (pages 4953–4964)

      Gabor Erdodi and Joseph P. Kennedy

      Article first published online: 12 SEP 2005 | DOI: 10.1002/pola.20978

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      The synthesis of a new type of amphiphilic conetwork consisting of well-defined hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments is described. The conetwork is ideal (the lengths of each PEG and PDMS chain segments, respectively, are identical) and tetrafunctional (exactly four chains emanate from each crosslink site). The synthesis of the conetworks was achieved by the use of a novel dual-purpose extender/crosslinker Y (bis[(dimethylsilyl)oxy]-[(etoxydimethylsilyl)- oxy]phenylsilane, (SiPh(SiH)2OEt)), in two steps: (1) Synthesis of a new linear random multiblock copolymer (AY)n(BY)m, where A is the hydrophilic PEG and B is the hydrophobic segment, and (2) Crosslinking the multiblocks by catalytic condensation of the SiOEt groups in the Y units. [A color version of the adjacent figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    25. Ideal tetrafunctional amphiphilic PEG/PDMS conetworks by a dual-purpose extender/crosslinker. II. Characterization and properties of water-swollen membranes (pages 4965–4971)

      Gabor Erdodi and J. P. Kennedy

      Article first published online: 12 SEP 2005 | DOI: 10.1002/pola.20977

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      Selective characteristics and properties of a series of membranes prepared of PEG/PDMS amphiphilic conetworks were investigated. Swelling characteristics indicate bicontinuous/bipercolating nano-morphology. Oxygen permeabilities of water-swollen membranes reflect those of the PEG and PDMS constituents. Tensile strengths, moduli, and elongations are appropriate for biological applications. The sketch shows the swelling behavior of conetworks in water and n-heptane, and those of the individual PEG and PDMS domains.

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      RAFT miniemulsion polymerization targeting to polymer of higher molecular weight (pages 4972–4979)

      Lei Yang, Yingwu Luo and Bogeng Li

      Article first published online: 9 SEP 2005 | DOI: 10.1002/pola.20968

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      A two-step semi-batch RAFT miniemulsion polymerization was found to be effective to synthesize higher molecular weight polystyrene with rather low PDI and low dead chain percentage.

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