Journal of Polymer Science Part A: Polymer Chemistry

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

1 April 2008

Volume 46, Issue 7

Pages 2309–2599

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. Creating microenvironments using encapsulated polymers (pages 2309–2315)

      Muris Kobašlija, Andrew R. Bogdan, Sarah L. Poe, Fernando Escobedo and D. Tyler Mcquade

      Article first published online: 22 FEB 2008 | DOI: 10.1002/pola.22630

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      Combining concepts from polymer chemistry and materials science, we present a general strategy for creating oil-in-oil microenvironments. The key to the strategy is the encapsulation of high-molecular weight polymers within polymeric microcapsules. By swelling the capsules in an appropriate binary solvent system that can be selected using standard chi-parameters, the polymers will phase separate in to polymer-rich domains within the interior of the microcapsules. Creating and using well-defined heterogeneous mixtures such as those found in biology remains a significant challenge. We propose that the reported microenvironments are another incremental step towards creating non-natural systems as complex and useful as a biological cell. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Synthesis and crosslinking behavior of a novel linear polymer bearing 1,2,3-triazol and benzoxazine groups in the main chain by a step-growth click-coupling reaction (pages 2316–2325)

      Atsushi Nagai, Yasutaka Kamei, Xiao-Shui Wang, Masaki Omura, Atsushi Sudo, Haruo Nishida, Eiichi Kawamoto and Takeshi Endo

      Article first published online: 22 FEB 2008 | DOI: 10.1002/pola.22558

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      The copper(I)-catalyzed alkyne-azide “click” coupling reaction was applied to synthesize a high-molecular weight prepolymer having benzoxazine moieties in the main chain. The obtained prepolymer underwent thermal crosslinking to afford the corresponding product, which exhibited a higher thermal stability than the prepolymer. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    3. Synthesis and properties of amino acid esters of hydroxypropyl cellulose (pages 2326–2334)

      Fareha Zafar Khan, Masashi Shiotsuki, Fumio Sanda, Yoshiyuki Nishio and Toshio Masuda

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22565

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      Hydroxypropyl cellulose (HPC), an organosoluble cellulosic of remarkable commercial and pharmaceutical significance, has been functionalized with amino acids, the basic building blocks of nature, to lead to the formation of novel biocompatible architectures. The amino acid esters of HPC were characterized by 1H NMR and IR spectroscopy and elemental analysis. The substitution of hydroxy protons of HPC by bulky amino acid functionalities resulted in the enhanced hydrophobicity (water insolubility) without any detriment of organosolubility. The incorporation of polar aminoalkanoyl moieties accompanied a significant increase in glass transition temperature transforming a rubbery starting material into almost glassy polymers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    4. Arborescent polystyrene-graft-poly(tert-butyl methacrylate) copolymers: Synthesis and enhanced polyelectrolyte effect in solution (pages 2335–2346)

      R. Andrew Kee and Mario Gauthier

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22566

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      Arborescent polyelectrolytes containing between 9 and 4500 poly(methacrylic acid) (PMAA) side chains were obtained by grafting “living” anionic poly(tert-butyl methacrylate) chains with Mw ≈ 5000 or 30,000 onto linear, comb-branched (G0), G1, and G2 bromomethylated arborescent polystyrene substrates. The copolymers, after deprotection and neutralization of the poly(methacrylic acid) segments, displayed enhanced molecular expansion as compared with linear PMAA analogues.

    5. Initiator selectivity during free radical copolymerizations of styrene and methyl methacrylate initiated by anaerobic copper(II) oxidation of carbon-13 labeled acetophenone (pages 2347–2356)

      H. James Harwood, Kristin McNamara, James J. Johnson and Faith J. Wyzgoski

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22567

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      NMR analysis was conducted on the chain ends of polystyrene, polyMMA, and styrene-MMA copolymers prepared by polymerizations initiated using 13C-labeled acetophenone. The NMR results of the copolymerization studies quantified the selectivity of the 13C-labeled-phenacyl radicals with respect to styrene versus MMA. Our studies showed that the phenacyl radical reacts 2.7 times faster with styrene than with MMA.

    6. Highly porous elastomer-silsesquioxane nanocomposites synthesized within high internal phase emulsions (pages 2357–2366)

      Jenny Normatov and Michael S. Silverstein

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22570

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      Highly porous, elastomeric nanocomposites were synthesized within the external phase of a high internal phase emulsion through copolymerization of 2-ethylhexyl acrylate, divinyl benzene, and a polyhedral oligomeric silsesquioxane (MACH-POSS) bearing seven cyclohexyl (non-reactive) groups and one propylmethacryl (reactive) group. The thermal and mechanical properties were varied through variations in the MACH-POSS content.

    7. Bipolar poly(p-phenylene vinylene)s bearing electron-donating triphenylamine or carbazole and electron-accepting quinoxaline moieties (pages 2367–2378)

      Panayiotis Karastatiris, John A. Mikroyannidis and Ioakim K. Spiliopoulos

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22571

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      Two new PPVs containing triphenylamine or carbazole as electron donor and quinoxaline as electron acceptor were synthesized. Their electrochemical properties and electroluminescent properties were investigated.

    8. Facile fabrication of hybrid nanoparticles surface grafted with multi-responsive polymer brushes via block copolymer micellization and self-catalyzed core gelation (pages 2379–2389)

      Yanfeng Zhang, Weiyin Gu, Hangxun Xu and Shiyong Liu

      Article first published online: 22 FEB 2008 | DOI: 10.1002/pola.22572

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      We report on the facile preparation of hybrid nanoparticles via a combination of block copolymer micellization and self-catalyzed core gelation. Poly(2-(dimethylamino)ethyl methacrylate)-b-poly(γ-methacryloxypropyltrimethoxysilane) (PDMA-b-PMPS) was synthesized via consecutive reversible addition-fragmentation chain transfer (RAFT) polymerizations. Micellization of the obtained amphiphilic diblock polymer in aqueous solution leads to the formation of nanoparticles consisting of PMPS cores and PDMA shells. Being a weak polybase, the PDMA corona can spontaneously catalyze the sol–gel reactions of trimethoxysilyl moieties within PMPS cores, leading to the formation of hybrid nanoparticles coated with PDMA brushes. They exhibit pH and thermoresponsiveness, and the swelling/collapse of them can be finely tuned with solution pH and temperatures.

    9. Tadpole-shaped amphiphilic copolymers prepared via RAFT polymerization and click reaction (pages 2390–2401)

      Gang-Yin Shi, Xue-Zhi Tang and Cai-Yuan Pan

      Article first published online: 22 FEB 2008 | DOI: 10.1002/pola.22573

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      A new approach for the synthesis of tadpole-shaped copolymers has been reported by the combination of RAFT polymerization and “click” chemistry. The synthetic strategy involves two main steps: synthesis of acetylene-terminated linear diblock copolymer, PS-b-PNIPAAM with an azido side group anchored at the junction between two blocks and intramolecular cyclization of the linear precursor under high dilution. The difference of surface property between tadpole-shaped polymer and its linear precursor was observed. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    10. UV-induced crosslinking of ring opening metathesis block copolymer micelles (pages 2402–2413)

      Martina Sandholzer, Sabine Bichler, Franz Stelzer and Christian Slugovc

      Article first published online: 22 FEB 2008 | DOI: 10.1002/pola.22574

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      Statistical and amphiphilic block copolymers bearing cinnamoyl groups were prepared by ROMP. The UV-induced [2+2] cycloaddition reaction of polymer bound cinnamic acid groups was studied in polymer thin films as well as in block copolymer micelles. For micelles obtained from polymers bearing 5 mol% or more cinnamoyl groups, the cross linking reaction proceeded smoothly, yielding in cross-linked particles which were stable in a non-selective solvent. This strategy of direct self assembly of block-copolymers in a selective solvent followed by ‘clean’ cross-linking, without the need for additional cross-linking reagents or cross-linking initiators, provides a straight forward approach towards ROMP-based polymeric nano-particles. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    11. Energetic polymer salts from 1-vinyl-1,2,4-triazole derivatives (pages 2414–2421)

      Hong Xue, Haixiang Gao and Jean'ne M. Shreeve

      Article first published online: 22 FEB 2008 | DOI: 10.1002/pola.22575

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      Energetic monomer and polymer salts obtained from 1-vinyl-1,2,4-triazole derivatives have been synthesized via polymerization of 1-vinyl-1,2,4-triazolium salts or by protonation of poly(1-vinyl-1,2,4-triazole) with inorganic or organic acids. Their physical and thermal properties have been investigated.

    12. Synthesis and characterization of fluorescently labeled core cross-linked star polymers (pages 2422–2432)

      Marisa Spiniello, Anton Blencowe and Greg G. Qiao

      Article first published online: 22 FEB 2008 | DOI: 10.1002/pola.22576

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      Fluorescently labeled core cross-linked star (CCS) polymers were prepared by atom transfer radical polymerization (ATRP) of living linear PMMA macroinitiator with divinylbenzene as the cross-linker and in the presence of the fluorescent monomer, 7-[4-(trifluoromethyl)coumarin] methacrylamide. The resulting CCS polymers were characterized using gel permeation chromatography, UV–visible and fluorescence spectrophotometry, and fluorescence microscopy. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    13. Quantitative IR characterization of urea groups in waterborne polyurethanes (pages 2433–2444)

      Ying Shi, Xiaoli Zhan, Zhenhuan Luo, Qinghua Zhang and Fengqiu Chen

      Article first published online: 22 FEB 2008 | DOI: 10.1002/pola.22577

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      A calibration curve was established with some polyurethane-urea standards, characterized by FTIR and 1H NMR, to investigate the side reaction, i.e., isocyanate-water reaction, during the polymerization of waterborne PUs. Several individual bands in amide I range were resolved by employing Fourier self-deconvolution (FSD) and Gaussian curve-fitting technique. A good correlation was evidenced between IR and 1H NMR measurements. From quantitative IR analysis of waterborne PUs prepared by miniemulsion polymerization of IPDI with diols, it was shown that the presence of a vinylic monomer restrained the isocyanate-water reaction by diluting the polyaddition medium, and the side reaction was influenced by the hydrophilicity of the vinylic monomers.

    14. Solvent-free and nonisocyanate melt transurethane reaction for aliphatic polyurethanes and mechanistic aspects (pages 2445–2458)

      P. Deepa and M. Jayakannan

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22578

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      A novel melt transurethane polycondensation route for polyurethanes under solvent-free and nonisocyanate condition was developed for soluble and thermally stable aliphatic or aromatic polyurethanes. The new transurethane process was investigated for A + B, A − A + B, and A − A + B − B (A-urethane and B-hydroxyl) -type condensation reactions, and also monomers bearing primary and secondary urethane or hydroxyl functionalities. The mechanistic aspects of the melt transurethane process and role of the catalyst were investigated using model reactions, 1H NMR, and MALDI-TOF MS. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    15. Synthesis and characterization of functional polyesters tailored for biomedical applications (pages 2459–2476)

      Benedetta Cerbai, Roberto Solaro and Emo Chiellini

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22579

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      This investigation was aimed at the preparation of polyesters containing side–chain reactive groups, potentially useful for targeted drug delivery and tissue engineering applications. Polyesters containing side-chain hydroxyl groups were synthesized by polyaddition of oxetanes and bisoxetanes with different carboxylic anhydrides and dicarboxylic acids, respectively. Polyesters containing either free or protected carboxyl groups were also obtained by homopolymerization and copolymerization of trisubstituted β-lactones. All polymeric materials were characterized by spectroscopic techniques, size exclusion chromatography, and thermal analysis. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    16. Breakdown kinetics of aggregates from poly(ethylene glycol-bl-propylene sulfide) di- and triblock copolymers induced by a non-ionic surfactant (pages 2477–2487)

      Simona Cerritelli, Diana Velluto, Jeffrey A. Hubbell and Antonella Fontana

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22580

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      Rate constants for Triton X-100-induced disruption of micelles from PEG-PPS block copolymers have been used as a measure of the stability of the polymeric aggregates and the affinity of the nonionic surfactant for the block copolymer. The hydrophobicity of the copolymer has been proven to drive the breakdown process. [Color figure can be viewed in the online issue, which is available at www. interscience.wiley.com.]

    17. Synthesis of poly(glycidol)-block-poly(N-isopropylacrylamide) copolymers using new hydrophilic poly(glycidol) macroinitiator (pages 2488–2499)

      Sebastian Mendrek, Aleksandra Mendrek, Hans-Jürgen Adler, Wojciech Walach, Andrzej Dworak and Dirk Kuckling

      Article first published online: 27 FEB 2008 | DOI: 10.1002/pola.22581

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      New, water soluble ω-(2-chloropropionyl) poly(glycidol) macroinitiators suitable for atom transfer radical polymerization were prepared. The final functionality of macroinitiators with different degree of polymerization varied in the range 85–95%. The ω-(2-chloropropionyl) poly(glycidol) with molecular weight 4300 g/mol was used for the polymerization of NIPAAm at room temperature in the DMF/water mixture yielding linear block copolymers with narrow molecular weight distribution and controlled composition. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    18. Initialization behavior at various target molecular weight RAFT-mediated methyl acrylate polymerizations (pages 2500–2509)

      Eric T. A. van den Dungen, Howard Matahwa, James B. McLeary, Ronald D. Sanderson and Bert Klumperman

      Article first published online: 5 FEB 2008 | DOI: 10.1002/pola.22582

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      The conversion of a RAFT-agent into its single monomer adduct was earlier termed initialization. For the first time, it is now shown that initialization is the cause of an induction period often observed at the start of a dithiobenzoate-mediated polymerization targeting higher molecular weights. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    19. N-vinylcaprolactam-based microgels: Synthesis and characterization (pages 2510–2524)

      Ainara Imaz and Jacqueline Forcada

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22583

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      Poly(N-vinylcaprolactam)-based microgels were synthesized in a batch reactor in order to analyze the effect of the cross-linker, initiator, surfactant, temperature, and VCL concentration on polymerization process and final microgels characteristics. To obtain information about the inner structure, semi-continuous polymerizations were carried out and the evolution of the average hydrodynamic particle diameters at different temperatures was investigated. The size and the swelling-de-swelling behavior as a function of the temperature of the medium can be tuned by modulating the reaction variables. Different swelling-de-swelling behaviors were observed depending on particles inner structure. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    20. Synthesis of polypeptides from activated urethane derivatives of α-amino acids (pages 2525–2535)

      Yasutaka Kamei, Atsushi Sudo, Haruo Nishida, Kiyoshi Kikukawa and Takeshi Endo

      Article first published online: 27 FEB 2008 | DOI: 10.1002/pola.22584

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      α-Amino acid derivatives, N-(4-nitrophenoxycarbonyl)-α-amino acids 1, were synthesized from L-amino acids with 4-nitrophenyl chloroformate. When 1 was heated at 60 °C in N,N-dimethylacetoamide (DMAc), it was smoothly converted into the corresponding polypeptides with releasing 4-nitrophenol and carbon dioxide. By using this method, their polycondensations of 1a and other monomers were also successfully carried out to obtain the corresponding statistic copolypeptides.

    21. Emulsion synthesis of nanoparticles containing PEDOT using conducting polymeric surfactant: Synergy for colloid stability and intercalation doping (pages 2536–2548)

      Chi-an Dai, Chun-jie Chang, Hung-yu Chi, Hung-ta Chien, Wei-fang Su and Wen-yen Chiu

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22585

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      Highly conductive composite nanoparticles containing PEDOT were synergistically synthesized by using conductive polymeric surfactant PTEB for emulsion polymerization. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    22. Fluorene-rich high performance polyesters: Synthesis and characterization of 9,9-fluorenylidene and 2,7-fluorenylene-based polyesters with excellent optical property (pages 2549–2556)

      Surasak Seesukphronrarak, Shinichi Kawasaki, Kana Kobori and Toshikazu Takata

      Article first published online: 27 FEB 2008 | DOI: 10.1002/pola.22586

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      Fluorene-rich aliphatic and aromatic polyesters PEs1−5 were synthesized in quantitative yields by the polycondensation of corresponding homoditopic alcohol and acid chloride monomers. The PEs showed high solubility to give the strong cast films with high transparency, and exhibited high refractive index values along with quite low degree of birefringence. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    23. Synthesis and modification of supports with an alkylamine and their use in albumin adsorption (pages 2557–2566)

      Cesar G. Gomez and Miriam C. Strumia

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22587

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      The morphological effect of polymeric networks modified with terminal amino groups was studied on the adsorption of bovine serum albumin. Poly(EGDMA-co-HEMA) beads were prepared by suspension polymerization using different EGDMA contents and stirring speeds. These base supports form porous meshes, where the void between densely crosslinked microspheres and their aggregates characterizes the pore. Protein enters the network up to a pore diameter equal to or higher than its conformation, and then the ammonium group adsorbs the protein by electrostatic interaction. This shows the importance of network morphology in the substrate adsorption degree.

    24. Synthesis and characterization of a starch-modified hydrogel as potential carrier for drug delivery system (pages 2567–2574)

      Adriano V. Reis, Marcos R. Guilherme, Thais A. Moia, Luiz H. C. Mattoso, Edvani C. Muniz and Elias B. Tambourgi

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22588

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      A new hydrogel composed of chemically modified starch (starch-M) was synthesized. The chemical modification of starch consisted of coupling C[BOND]C bounding coming from glycidyl methacrylate onto polysaccharide structure. The hydrogel was prepared by cross-linking polymerization of the starch-M. The starch-M hydrogel shows morphology clearly different from that of the raw starch film. Dynamics of swelling demonstrated that the water penetration mechanism into gel is controlled by Fickian diffusion, resulted of the physical–chemical interactions between solvent and hydrogel.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. You have free access to this content
      Facile room temperature RAFT polymerization via redox initiation (pages 2575–2580)

      Haiting Zheng, Wei Bai, Keliang Hu, Ruke Bai and Caiyuan Pan

      Article first published online: 5 FEB 2008 | DOI: 10.1002/pola.22590

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      Facile room temperature RAFT polymerizations of methyl acrylate and styrene have been successfully performed using the redox system of BPO and DMA as the initiator in the presence of benzyl 1H-imidazole-1-carbodithioate. Since this redox initiator is available, much cheaper, and has large decomposition rate constant, we believe it will make the room temperature RAFT polymerization more promising and attractive at both academic and industrial standpoints.

    2. You have free access to this content
      Dendritic networks containing polyhedral oligomeric silsesquioxane (POSS) and carborane clusters (pages 2581–2587)

      Manoj K. Kolel-Veetil, Dawn D. Dominguez and Teddy M. Keller

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22601

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      Dendritic hydrosilated network with exceptional thermo-oxidative stability containing POSS and carborane nanoclusters was synthesized from octasilane-POSS (1) and vinyl-terminated carboranylenesiloxane (2). A variant of the product, containing additional structurally reinforcing [BOND]Si[BOND]O[BOND]Si[BOND] bonds, was formed by the concomitant hydrosilation between 1 and 2 and the oxidation/hydrolysis/condensation reaction of a stoichiometric excess of 1 in the presence of the Karstedt catalyst, and triethylamine and water cocatalysts. The enhanced thermal and thermo-oxidative stabilities and structural rigidity of the reinforced network containing the additional [BOND]Si[BOND]O[BOND]Si[BOND] bonds were reflected in its higher char yields and storage/loss moduli.

  3. Notes

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. You have free access to this content
      A new series of cyclic 5-membered dithiocarbonates having urethane tether: Application as an adhesion promoter to epoxy-amine curing system (pages 2588–2592)

      Atsushi Sudo, Suguru Motokucho and Takeshi Endo

      Article first published online: 5 FEB 2008 | DOI: 10.1002/pola.22589

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      A new series of 5-membered cyclic dithiocarbonates having urethane tether (DTC-urethane) were synthesized and employed as additives for epoxy-amine curing system to improve its adhesion performance in steel-bonding application.

    2. You have free access to this content
      Polymerization of aliphatic alkynes with heterogeneous Mo catalysts supported on mesoporous molecular sieves (pages 2593–2599)

      Hynek Balcar, Pavel Topka, Jan Sedláček, Jiří Zedník and Jiří Čejka

      Article first published online: 25 FEB 2008 | DOI: 10.1002/pola.22600

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      Aliphatic 1-alkynes were polymerized over heterogeneous catalysts prepared by supporting (i) MoO3 and (ii) Mo (=CHCMe2Ph)(=N-2,6-i-Pr2C6H3)[OCMe(CF3)2]2 on mesoporous molecular sieves MCM-41, MCM-48, and SBA-15. Poly(n-alkylacetylene)s of Mw in the range from 5,000 to 30,000 and poly(tert-butylacetylene) of Mw ∼300,000 were prepared in yields ranging from 11 to 64%. Polyacetylene type structure (conjugated main chain and alkyl pendant groups) was confirmed by 1H NMR. Both catalysts enabled easy product separation delivering polymers free of catalyst residues.

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