Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

15 August 2003

Volume 41, Issue 16

Pages 2425–2606

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      The fast and the curious: High-throughput experimentation in synthetic polymer chemistry (pages 2425–2434)

      Richard Hoogenboom and Ulrich S. Schubert

      Article first published online: 25 JUN 2003 | DOI: 10.1002/pola.10788

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      The application of automated synthetic parallel methods in polymer chemistry is described. A brief overview of all different polymerization techniques that have been used is provided. Furthermore, the equipment and methodologies that were used in our approach for automated parallel polymerization reactions are discussed followed by detailed insight into recent developments on automated cationic ring-opening polymerization, atom transfer radical polymerization, and emulsion polymerizations.

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    1. Functionalization of polymeric organolithium compounds with formaldehyde (pages 2435–2453)

      Roderic P. Quirk, Ya Guo, Chrys Wesdemiotis and Mark A. Arnould

      Article first published online: 24 JUN 2003 | DOI: 10.1002/pola.10779

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      Functionalizations of poly(styryl)lithium (PSLi), poly(butadienyl)-lithium (PBDLi), and poly(isoprenyl)lithium (PILi) with formaldehyde were investigated in benzene solution at room temperature. Dimer and unfunctionalized products in addition to the expected products were found in the PSLi functionalization with formaldehyde. The byproducts were analyzed by 1H NMR, 13C NMR, SEC, and MALDI-TOF MS and showed evidence for Cannizzaro reactions and electron transfer reactions. Reactions of PBDLi and PILi with formaldehyde effected quantitative functionalizations as determined by SEC, 1H NMR, 13C NMR, MALDI-TOF MS, quantitative column chromatography, and end-group titration.

    2. Graftlike interpolymer complexes from poly(2-vinylpyridine) and end-sulfonic acid polystyrene and polyisoprene: Intermediates to noncovalently bonded block copolymer-like micelles (pages 2454–2461)

      Katerina Orfanou, Dimitra Topouza, George Sakellariou and Stergios Pispas

      Article first published online: 24 JUN 2003 | DOI: 10.1002/pola.10791

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      The complexation between narrow molecular weight distribution poly(2-vinylpyridine) (P2VP) and polystyrene (suPS) or polyisoprene (suPI) end-functionalized with one sulfonate group was examined in tetrahydrofuran dilute solutions by a combination of static and dynamic laser light scattering. When suPI was used for complex formation, it was possible to prepare block copolymer-like micelles when transferring the P2VP/suPI blend solutions in a selective solvent such as decane, which dissolves PI chains but not P2VP. The non-covalent-bonded polymeric micelle characteristics were investigated in connection with sulfonate/2-vinylpyridine units ratio as well as temperature.

    3. Mechanical property and biodegradability of solution-cast films prepared from amphiphilic polylactide-grafted dextran (pages 2462–2468)

      Tatsuro Ouchi, Tomohiro Kontani and Yuichi Ohya

      Article first published online: 24 JUN 2003 | DOI: 10.1002/pola.10783

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      Polylactide (PLA)-grafted dextran was synthesized with a trimethylsilyl protection method to produce novel biodegradable, biomedical materials. The cast films prepared from PLA-grafted dextrans with various lengths and numbers of graft chains exhibited lower glass-transition temperatures, melting temperatures, and crystallinity as well as higher viscosity properties as compared with poly-L-lactide film. Furthermore, the degradation rate was investigated from the points of weight loss of PLA-grafted dextran film and molecular weight reduction of PLA-grafted dextran. It could be adjusted by controlling the molecular architecture such as length and number of graft chains.

    4. Seeded semicontinuous emulsion copolymerization of methyl methacrylate, butyl acrylate, and phosphonated methacrylates: Kinetics and morphology (pages 2469–2480)

      Manuel Gaboyard, Thomas Jeanmaire, Christian Pichot, Yves Hervaud and Bernard Boutevin

      Article first published online: 25 JUN 2003 | DOI: 10.1002/pola.10784

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      The copolymerization of methyl methacrylate (MMA), butyl acrylate (BuA), and phosphonated methacrylates (MAPHOS) by seeded semicontinuous emulsion polymerization was investigated. Effects on kinetics, molecular weight distribution, particle growth, and surface morphology were studied with respect to changes in the amount and the nature of phosphonated monomers.

    5. Synthesis and characterization of phthalazinone containing poly(arylene ether)s via a novel N–C coupling reaction (pages 2481–2490)

      S. J. Wang, Y. Z. Meng, S. C. Tjong, A. R. Hlil and A. S. Hay

      Article first published online: 25 JUN 2003 | DOI: 10.1002/pola.10792

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      High-molecular-weight poly(phthalazinone)s with very high glass-transition temperatures (Tg's) were synthesized via a novel N–C coupling reaction. New bisphthalazinones were synthesized from 2-(4-chlorobenzoyl) phthalic acid and activated aryl halide in a dipolar aprotic solvent in the presence of potassium carbonate. The highest Tg of poly(phthalazinone)s was 297 °C. The poly(phthalazinone)s were soluble in common solvents such as chloroform and can be cast into flexible films from solution.

    6. Diffusion coefficients of the monomer and oligomers in hydroxyethyl methacrylate (pages 2491–2501)

      Jelica Strauch, James McDonald, Bogdan E. Chapman, Philip W. Kuchel, Brian S. Hawkett, G. Evan Roberts, Matthew P. Tonge and Robert G. Gilbert

      Article first published online: 26 JUN 2003 | DOI: 10.1002/pola.10789

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      Diffused coefficients Di of i-meric oligomers were obtained by pulsed-field gradient NMR in rubbery systems comprising polymer, monomer, and oligomers (synthesized using cobalt catalytic chain transfer agent) for 2-hydroxyethyl methacrylate (HEMA), with polymer weight-fraction 0 ≤ fp ≤ 0.4. The Di were much smaller than for monomers such as MMA, ascribed to hydrogen bonding in HEMA, and fitted the empirical relation Di(fp)/D1(fp) ≈ imath image, which also fits corresponding data for styrene and various methacrylates. This relation is useful for taking into account chain-length dependent termination (dominated by diffusion of small chains) and the gel effect when modeling free-radical polymerizations.

    7. Synthesis of conjugated copolymers containing phenothiazinylene vinylene moieties and their electrooptic properties (pages 2502–2511)

      Yoon Soo Han, Sang Dae Kim, Lee Soon Park, Dong Uk Kim and Younghwan Kwon

      Article first published online: 26 JUN 2003 | DOI: 10.1002/pola.10793

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      Four different types of conjugated copolymers, consisting of alternating structures of phenothiazinylene vinylene and phenylene vinylene derivatives such as phenylene vinylene, 1,1′-biphenyl-4,4′-ylene vinylene, 2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene, and 9,10-anthrylene vinylene, were prepared by Horner–Emmons condensation between appropriate diphosphonates and dialdehydes. Single-layer and double-layer light-emitting diodes were fabricated with the synthesized conjugated polymers, and their electroluminescent properties were investigated.

    8. Synthesis and characterization of chiral liquid-crystalline polyesters containing sugar-based diols via melt polymerization (pages 2512–2520)

      Qin Lin, Jeremy Pasatta and Timothy E. Long

      Article first published online: 7 JUL 2003 | DOI: 10.1002/pola.10787

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      Liquid-crystalline (LC) polyesters based on hexanediol or butanediol, dimethyl 4,4′-biphenyldicarboxylate, and a sugar-based diol, isosorbide or isomanide, were prepared with conventional melt polymerization. The lined focal conic fan textures, typical indications of a chiral smectic C LC phase, were observed upon the shearing of the LC melt under polarized light microscopy.

    9. Liquid-crystalline thermosets by the curing of dimeric liquid-crystalline epoxyimine monomers with 2,4-toluene diisocyanate (pages 2521–2530)

      David Ribera, Angels Serra and Ana Mantecón

      Article first published online: 7 JUL 2003 | DOI: 10.1002/pola.10794

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      We used two methods to form liquid-crystalline thermosets from liquid-crystalline epoxy resins with dimeric architectures and nonmesomorphic diisocyanates. The first method was a two-step process in which liquid-crystalline oligomers were first formed by the reaction of epoxides and 2,4-toluene diisocyanate (TDI) in stoichiometric proportions and were then reacted in the mesophase range to fix ordered networks. The second method was a single process in which a tertiary amine as a catalyst was added to stoichiometric mixtures of diepoxides and TDI. Crosslinking by diisocyanates highlighted the significance of the polarization of the mesogen in the fixation of ordered networks.

    10. 13Carbon nuclear magnetic resonance of ethylene–propylene–1-decene terpolymers (pages 2531–2541)

      Fernanda F. Nunes Escher, Griselda Barrera Galland and Márcio Ferreira

      Article first published online: 26 JUN 2003 | DOI: 10.1002/pola.10790

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      A complete 13C NMR characterization of ethylene–propylene–1-decene terpolymers was performed qualitatively and quantitatively. A detailed study of the 13C NMR chemical shifts, triad sequence distributions, monomer average sequence lengths, and reactivity ratios for these terpolymers is presented.

    11. Synthesis of miktoarm star and miktoarm star block copolymers via a combination of atom transfer radical polymerization and stable free-radical polymerization (pages 2542–2548)

      Cigdem Celik, Gurkan Hizal and Umit Tunca

      Article first published online: 7 JUL 2003 | DOI: 10.1002/pola.10798

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      A trifunctional initiator, 2-phenyl-2-[(2,2,6,6-tetramethyl)-1-piperidinyloxy] ethyl 2,2-bis[methyl(2-bromopropionato)] propionate (1), was synthesized and used for the synthesis of miktoarm star AB2 and miktoarm star block AB2C2 copolymers via a combination of stable free-radical polymerization and atom transfer radical polymerization in a two-step or three-step reaction sequence, respectively. Miktoarm star (PSt)(PtBA)2 [where PtBA is poly(tert-butyl acrylate)] and star block copolymer (PSt)(PtBA)2(PMMA)2 [where PMMA is poly(methyl methacrylate)], with controlled molecular weights and moderate polydispersities (weight-average molecular weight/number-average molecular weight < 1.38), were obtained.

    12. Self-curable polyester by a reaction of glycidol with maleic anhydride (pages 2549–2555)

      Niyazi Bicak, Bunyamin Karagoz and Umit Tunca

      Article first published online: 7 JUL 2003 | DOI: 10.1002/pola.10797

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      The controlled reaction of equimolar quantities of maleic anhydride and glycidol in dimethoxyethane gives soluble polyesters with one hydroxyl group in each repeating unit. The reaction proceeds with stepwise ring opening of the components and gives highly viscous clear solutions in relatively short periods. In the first step, monomaleate ester formation takes place around 80 °C. The ring opening of the oxirane group is the second step, and it occurs at 120 °C. The overall reaction is the formation of soluble polyesters with moderate molecular weights (6000–18,000), without the elimination of water.

    13. Synthesis and characterization of second-generation S,S-dialkyl-S-(dimethylhydroxyphenyl)sulfonium salt photoinitiators (pages 2556–2569)

      James V. Crivello and Jinseo Ahn

      Article first published online: 7 JUL 2003 | DOI: 10.1002/pola.10801

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      A new, simplified method for the synthesis of S,S-dialkyl-S-(dimethylhydroxyphenyl)sulfonium salt cationic photoinitiators has been developed. This novel method has successfully been used for the preparation of S,S-dialkyl-S-(3,5-dimethyl-4-hydroxyphenyl)sulfonium and S,S-dialkyl-S-(3,5-dimethyl-2-hydroxyphenyl)sulfonium salts showing a wide variation in the length and structure of the alkyl chains on the positively charged sulfur atom and with different anions.

    14. Photoinduced and thermally induced cationic polymerizations using S,S-dialkyl-S-(3,5-dimethylhydroxyphenyl)sulfonium salts (pages 2570–2587)

      James V. Crivello and Jinseo Ahn

      Article first published online: 7 JUL 2003 | DOI: 10.1002/pola.10800

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      A study of the photoinitiated and thermally initiated cationic polymerizations of several monomer systems with S,S-dialkyl-S-(3,5-dimethylhydroxyphenyl)sulfonium salt (HPS) photoinitiators bearing different lengths of alkyl chains on the sulfur atom has been conducted. HPS photoinitiators are capable of photoinitiating the cationic polymerization of a wide variety of epoxy and vinyl ether monomers directly on irradiation with short-wavelength UV light or at longer wavelengths with aryl ketone photosensitizers.

    15. Synthesis and characterization of crosslinked uniform polymeric microspheres containing a polyimide prepolymer by a new emulsification process (pages 2588–2598)

      Guang-Hui Ma, Junichiro Fujiwara, Zhi-Guo Su and Shinzo Omi

      Article first published online: 11 JUL 2003 | DOI: 10.1002/pola.10795

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      A highly crosslinked poly(styrene–divinyl benzene–trimethyolpropane trimethacrylate) microsphere containing a polyimide prepolymer (PIP) was prepared by a new emulsification method, Shirasu porous glass membrane emulsification, and a subsequent radical suspension polymerization. A trifunctional crosslinker, trimethyol propane trimethacrylate (TMPTMA), was added to enhance the destructive strength of the microsphere, and PIP was incorporated into the microsphere to provide an adhesion force by a known self-curing reaction at 220 °C. A particle with a narrow size distribution of around 12% was obtained. The destructive strength increased with increases in the feed amounts of TMPTMA and PIP. The obtained highly crosslinked uniform microsphere containing PIP has potential applications in liquid-crystal displays.

    16. Synthesis and properties of bismaleimide-modified novolak resin/silsesquioxane nanocomposites (pages 2599–2606)

      Guotao Lu, Ying Huang, Yehai Yan, Tong Zhao and Yunzhao Yu

      Article first published online: 11 JUL 2003 | DOI: 10.1002/pola.10786

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      Bismaleimide-modified novolak resin/silsesquioxane (BMI-PN/SiO3/2) nanocomposites were prepared by the sol–gel process.

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