Journal of Polymer Science Part A: Polymer Chemistry

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

15 July 2001

Volume 39, Issue 14

Pages 2351–2556

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communication
    5. Articles
    1. You have free access to this content
      Using polymers to control substrate, ligand, or catalyst solubility (pages 2351–2363)

      David E. Bergbreiter

      Article first published online: 22 MAY 2001 | DOI: 10.1002/pola.1212

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      Methods by which polymers engineer solubility for bound reagents, substrates, and catalysts are reviewed. Five approaches are described. The first uses heat to dissolve a polymer and cooling to precipitate it. A second scheme uses polymers that dissolve cold and precipitate or phase separate hot. The third uses an amphoteric polymer whose solubility depends on pH. The fourth method uses solvent mixtures whose miscibilities change with temperature, where one phase in the biphasic mixture preferentially dissolves a polymer. The last uses immiscible solvents, one of which dissolves the polymer. In every case, the polymer-bound species is used under homogeneous conditions but recovered under biphasic conditions.

    2. You have free access to this content
      Polymer-supported reagents, catalysts, and sorbents: Evolution and exploitation—A personalized view (pages 2364–2377)

      D. C. Sherrington

      Article first published online: 25 MAY 2001 | DOI: 10.1002/pola.1213

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      Polymer-supported chemistry is now ubiquitous in organic synthetic laboratories worldwide, but has not always been so. This Highlight article charts the development of the area, and in particular describes the evolution of polymer-supported reagents, catalysts, and sorbents, and their exploitation both on a small and large scale.

  2. Articles

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    2. Highlights
    3. Articles
    4. Rapid Communication
    5. Articles
    1. Cobalt-mediated catalytic chain-transfer polymerization (CCTP) in water and water/alcohol solution (pages 2378–2384)

      David M. Haddleton, Estelle Depaquis, Elizabeth J. Kelly, Dax Kukulj, Stuart R. Morsley, Stefan A. F. Bon, Michael D. Eason and Andrew G. Steward

      Article first published online: 25 MAY 2001 | DOI: 10.1002/pola.1214

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      A range of monomers has been polymerized by aqueous solution catalytic chain-transfer polymerization, methacrylic acid, 2-aminoethyl methacrylate hydrochloride, 2-hydroxyethyl methacrylate, 2-methacryloxyethyl phosphoryl choline, glycerol monomethyl methacrylate, and 3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-D-glucofuranose. High conversion to macromonomer is observed with observed chain-transfer constants of approximately 1000 under an appropriate catalyst feed profile.

    2. Design and synthesis of highly reactive photopolymerizable epoxy monomers (pages 2385–2395)

      James V. Crivello and Ricardo Acosta Ortiz

      Article first published online: 25 MAY 2001 | DOI: 10.1002/pola.1215

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      The synthesis of a series of novel cationically photopolymerizable epoxide monomers bearing acetal and ether groups that can stabilize free radicals was carried out. These monomers display enhanced reactivity in cationic photopolymerization because of their ability to facilitate the free-radical-induced decomposition of diaryliodonium salt photoinitiators.

    3. Ferrocene-based organophosphorus liquid–crystalline polymers: Synthesis and characterization (pages 2396–2403)

      S. Senthil and P. Kannan

      Article first published online: 25 MAY 2001 | DOI: 10.1002/pola.1216

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      Liquid–crystalline ferrocene-containing polyphosphate and phosphonate esters were synthesized by the solution polycondensation method and confirmed using various spectroscopic techniques. The char yields of the synthesized polymers were much higher than that of similar nonphosphorus polymers reported in the literature. Thermal analysis confirmed our predictions over the liquid–crystalline property, glass-transition temperature, isotropization temperature, and stability of the polymers. The effect of substitution on the side chain of the polymers has also been discussed.

    4. Soluble fluorinated polyimides derived from 1,4- (4′-aminophenoxy)-2-(3′-trifluoromethylphenyl)benzene and aromatic dianhydrides (pages 2404–2413)

      Hongwei Zhou, Jingang Liu, Zhiguo Qian, Shuying Zhang and Shiyong Yang

      Article first published online: 25 MAY 2001 | DOI: 10.1002/pola.1217

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      New fluorinated aromatic polyimides were synthesized via the polycondensation of 1,4-(4′-aminophenoxy)-2-(3′-trifluoro methyl phenyl)benzene with various aromatic dianhydrides. The polyimides had good solubility in common organic solvents and showed exceptional thermal stability and mechanical properties. Low dielectric constants (2.55–2.71 at 1 MHz), low refractive indices, and low water absorption were also observed.

    5. Novel synthesis of polyimide–polyhybridsiloxane block copolymers via polyhydrosilylation: Characterization and physical properties (pages 2414–2425)

      S. Andre, F. Guida-Pietrasanta, A. Rousseau and B. Boutevin

      Article first published online: 25 MAY 2001 | DOI: 10.1002/pola.1218

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      This study investigated a novel route to obtain perfectly alternating polyimide–polyhybridsiloxane block copolymers by polyhydrosilylation. The siloxane block was called hybrid because an alkyl spacer was included between two silicon atoms. The use of hybrid siloxane as a soft segment brought better thermostability and better chemical resistance in comparison with a classic siloxane with [BOND]Si(CH3)2[BOND] O[BOND] units. Polyhydrosilylation was performed to elaborate high-performance thermoplastic elastomers from allyl telechelic polyimides and hydrosilane telechelic polyhybridsiloxane.

  3. Rapid Communication

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communication
    5. Articles
    1. Preparation of AB-type diblock copolymers containing poly-(2,6-dimethyl-1,4-phenylene oxide) and methyl methacrylate or styrene blocks (pages 2426–2429)

      G. Hizal, N. Bicak and U. Tunca

      Article first published online: 29 MAY 2001 | DOI: 10.1002/pola.1219

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      The poly-(2,6-dimethyl-1,4-phenylene oxide) (PPO) oligomers with activated halogen end groups were used as macroinitiators for atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) and styrene (St). In the former case, AB-type block copolymers with well-defined PPO and MMA blocks were obtained. However, in the case of ATRP of St in diphenylether solution, slow polymerization was observed so that conversion only reached up to 6% for 4 h.

  4. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communication
    5. Articles
    1. Melt-processable poly(oxyphenylalkanoate): Synthesis, properties, and in vitro degradation of poly(4-oxyphenylacetate) (pages 2430–2443)

      V. S. Prasad, C. K. S. Pillai and H. R. Kricheldorf

      Article first published online: 25 MAY 2001 | DOI: 10.1002/pola.1220

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      The homopolyester of 4-hydroxyphenylacetic acid (HPAA) was synthesized by one-pot, slurry-melt, and acidolysis melt polymerization techniques and was characterized for its thermal and phase behavior. The acidolysis melt polymerization of the pure acetoxy derivative of HPAA was the best method for the preparation of high molecular weight poly(4-oxyphenylacetate) (polyHPAA). PolyHPAA was characterized by Fourier transform infrared, polarizing light microscopy, differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray diffraction, and scanning electron microscopy methods. The in vitro degradability of the polymer indicated a possible biomedical application of polyHPAA as a substitute for poly(hydroxyalkanoate)s with a higher melting temperature.

    2. Photoinitiated polymerization of methacrylic monomers in a polybutadiene matrix (PB): Kinetic, mechanistic, and structural aspects (pages 2444–2453)

      J. L. Mateo, M. Calvo and P. Bosch

      Article first published online: 29 MAY 2001 | DOI: 10.1002/pola.1221

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      The kinetics and mechanism of the photoinitiated polymerization of tetrafunctional and difunctional methacrylic monomers in a polybutadiene matrix (PB) have been studied. For the PB-1,6-hexanediol timethacylate (PB-HDDMA) system, the reaction diffusion controls the termination process only after approximately 10% conversion is reached. Before reaching 10% conversion, the behavior observed can be better explained by a combination of segmental diffusion-controlled (autoaccelerated) and reaction-diffusion mechanisms. For the PB-2-ethylhexyl methacrylate (PB-EHMA) system, the termination mechanism is principally diffusion-controlled from the beginning of the polymerization for monomer concentrations below 30–40%, and for higher monomer concentrations, a standard termination mechanism takes place (kt ≈ 106) at low double-bond conversions, which are diffusion-controlled for high conversions (>40%).

    3. Poly(pyridinium salt)s with stilbene or distyrylbenzene chromophores (pages 2454–2462)

      Ioakim K. Spiliopoulos and John A. Mikroyannidis

      Article first published online: 29 MAY 2001 | DOI: 10.1002/pola.1222

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      New soluble and photoluminescent poly(pyridinium salt)s were synthesized and characterized. They were amorphous and soluble in polar aprotic solvents. Their glass-transition temperatures ranged from 59 to 123 °C. The polymers showed violet-blue fluorescence in solution with photoluminescence (PL) maxima at 408–416 nm and violet-green fluorescence in thin film with PL maxima at 454–523 nm.

    4. Synthesis of high molecular weight trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) by the acyclic diene metathesis polymerization using molybdenum catalysts (pages 2463–2470)

      Kotohiro Nomura, Hisao Morimoto, Yukio Imanishi, Zoubir Ramhani and Yves Geerts

      Article first published online: 30 MAY 2001 | DOI: 10.1002/pola.1223

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      High molecular weight trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) was prepared under reduced pressure in the presence of a well-defined Schrock-type initiator, Mo(CHCMe2Ph)(N-2,6-Me2C6H3)[OCMe(CF3)2]2, in toluene. The effect of initial monomer concentration was found to be an important key factor for preparing high molecular weight polymers with unimodal molecular weight distributions.

    5. 1H NMR study of the kinetics of substituted aniline polymerization. I. Homopolymerization of 2-methoxyaniline (pages 2471–2481)

      Ida Mav and Majda Žigon

      Article first published online: 30 MAY 2001 | DOI: 10.1002/pola.1224

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      We studied the kinetics of the chemical homopolymerization of 2-methoxyaniline (OMA) under various reaction conditions with 1H NMR spectroscopy. We used the same semiempirical kinetic model used for aniline (ANI) homopolymerization to evaluate the experimental data. The OMA polymerization rate was lower than that of ANI. It increased with increasing oxidant and initial monomer concentrations and with the reaction temperature, but no uniform relationship was observed for the acid concentrations.

    6. 1H NMR study of the kinetics of substituted aniline polymerization. II. Copolymerization of 2-methoxyaniline and 3-aminobenzenesulfonic acid (pages 2482–2493)

      Ida Mav and Majda Žigon

      Article first published online: 30 MAY 2001 | DOI: 10.1002/pola.1225

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      We investigated the kinetics of the oxidative chemical copolymerization of 2-methoxyaniline (OMA) and 3-aminobenzenesulfonic acid (MA) with 1H NMR spectroscopy. We adapted a semiempirical kinetic model for the special case of copolymerization characterized by a large difference in the reactivities of the monomers involved. The influence of the reactions conditions on the OMA polymerization kinetics was similar to the influence on its homopolymerization. MA began to polymerize after OMA propagation began; the MA initiation rate, propagation rate, and end conversion were lower than those of OMA. Higher oxidant or MA concentrations, higher temperatures, and a 1 M DCl concentration favored MA conversion.

    7. Synthesis and stability of linear and star polymers containing [C60] fullerene (pages 2494–2507)

      Dimitris Pantazis, Stergios Pispas and Nikos Hadjichristidis

      Article first published online: 31 MAY 2001 | DOI: 10.1002/pola.1226

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      Linear and symmetric star block copolymers of styrene and isoprene connected to [C60] fullerene with a polyisoprene block were synthesized by anionic polymerization and appropriate linking postpolymerization chemistry. Degradation of the fractionated star-shaped copolymers was observed after storage for 2 months at 4 °C, unlike for nonfractionated material, which was stable. Linear copolymers end-capped, through [BOND]N<, with C60, as well as star polymers with PS block connected to C60, were also stable. Possible reasons are discussed.

    8. New biodegradable polymers from renewable sources: Polyester-carbonates based on 1,3-propylene-co-1,4-cyclohexanedimethylene succinate (pages 2508–2519)

      Yan Liu, Elisabetta Ranucci, Margaretha Söderqvist Lindblad and Ann-Christine Albertsson

      Article first published online: 31 MAY 2001 | DOI: 10.1002/pola.1227

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      The chain-extension reaction of α,ω-dihydroxy-terminated (1,3-propylene-co-1,4-cyclohexanedimethylene succinate)s via chloroformate synthesis is reported. The results obtained prove the feasibility to use monomers derived from renewable sources to build up high molecular weight polymers having an aliphatic/alicyclic polyester-carbonate structure. The new copolymers were semicrystalline with low glass-transition temperatures. On the basis of what generally was observed in the case of related materials, they are expected to be biodegradable in different environmental conditions.

    9. One-step preparation of polyurethane dispersions by miniemulsion polyaddition (pages 2520–2524)

      Franca Tiarks, Katharina Landfester and Markus Antonietti

      Article first published online: 1 JUN 2001 | DOI: 10.1002/pola.1228

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      The application of the miniemulsion process to synthesize polyurethane dispersions with diameters of about 200 nm in a one-step procedure, free of molecular weight restrictions, is described. With IR and NMR spectroscopy, it is shown that the reaction of the diisocyanate with the diol is the main reaction, whereas the reaction with water is only a side reaction. Differential scanning calorimetry measurements and transmission electron microscopy are used to characterize both polymer and latex properties.

    10. Water-soluble acrylamide copolymers. IX. Preparation and characterization of the cationic derivatives of poly(acrylamide-co-n,n-dimethylacrylamide), poly(acrylamide-co-methacrylamide), and poly(acrylamide-co-n-t-butylacrylamide) (pages 2525–2535)

      Keith A. Klimchuk, Martin B. Hocking and Stephen Lowen

      Article first published online: 1 JUN 2001 | DOI: 10.1002/pola.1229

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      This article extends the preparative details of a series of nonionic copolymers of acrylamide with N,N-dimethylacrylamide, methacrylamide, and N-t-butylacrylamide to the synthesis of cationic derivatives of these new copolymers. The described procedures gave products with cationicities of 14–26 mol %. We measured the mean squared radii of gyration and intrinsic viscosities of aqueous solutions of these products at several different pHs and NaCl concentrations to compare these values with those determined for the nonionic precursors and related commercial cationic polymers. Because the molecular weights of the examples measured varied widely, it was difficult to establish definite trends. However, the large values obtained for the mean squared radii of gyration and intrinsic viscosities, relative to the nonionic precursors of these polymers, demonstrated that the charged groups had a qualitatively greater effect on polymer extension than the nonpolar bulky groups.

    11. Hyperbranched aromatic poly(ether imide)s: Synthesis, characterization, and modification (pages 2536–2546)

      Fang-Iy Wu and Ching-Fong Shu

      Article first published online: 1 JUN 2001 | DOI: 10.1002/pola.1230

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      An AB2 monomer containing a pair of phenolic groups and an aryl fluoro moiety was prepared. The nucleophilic substitution of the fluoride by the phenolate groups, activated by the imide ring, resulted in the formation of an ether linkage and, subsequently, a hyperbranched poly(ether imide) containing terminal phenolic groups. As determined by a combination of model compound studies and 1H NMR integration data, the degree of branching was approximately 55%. The terminal phenolic groups in the hyperbranched poly(ether imide) were easily modified. The nature of the chain-end groups significantly influenced physical properties, such as the glass-transition temperature and the solubility of the hyperbranched poly(ether imide)s.

    12. Methyl methacrylate emulsion polymerization at low monomer concentration: Kinetic modeling of nucleation, particle size distribution, and rate of polymerization (pages 2547–2556)

      Jorge Herrera-Ordóñez and Roberto Olayo

      Article first published online: 4 JUN 2001 | DOI: 10.1002/pola.1231

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      The results of a mathematical model developed in our previous work are discussed and compared against experimental data of final number (N) and size distribution of particles (PSD) and the rate of polymerization of methyl methacrylate (MMA) emulsion polymerization above the critical micelle concentration of the surfactant. The proper modeling of the compartmentalization effect and the size dependence of the kinetic rate coefficients (without considering the limited coagulation of primary particles) allow one, for example, to qualitatively predict bimodal PSDs as shown in the figure. On the basis of the model results, new hypotheses that explain this and other unusual experimental data of MMA batch polymerization are proposed.

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