Journal of Polymer Science Part A: Polymer Chemistry

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

1 January 2002

Volume 40, Issue 1

Pages 1–178

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      Synthesis and self-assembly of fluorinated block copolymers (pages 1–8)

      Marc A. Hillmyer and Timothy P. Lodge

      Version of Record online: 5 NOV 2001 | DOI: 10.1002/pola.10074

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      Fluorinated block copolymers combine the unique properties of fluoropolymers and the intriguing self-assembly of hybrid macromolecules. The preparation of the title molecules by selective fluorination procedures and the effect of fluorine incorporation on the material thermodynamics are presented. The role of fluorination in determining block copolymer interactions in both the solid state and in solution and in ultimately exploiting fluorination to produce novel, higher order structures is central to our research efforts.

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    1. Oxidative copolymerization of indene with p-tert-butylstyrene: Synthesis, characterization, thermal analysis, and reactivity ratios (pages 9–18)

      Priyadarsi De and D. N. Sathyanarayana

      Version of Record online: 5 NOV 2001 | DOI: 10.1002/pola.10075

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      Copolyperoxides of indene and p-tert-butylstyrene were synthesized by free-radical-initiated oxidative copolymerization. The compositions of the copolyperoxides, obtained from 1H and 13C NMR spectra, led to the determination of the reactivity ratios. The copolyperoxides underwent highly exothermic degradation. The activation energy for the thermal degradation suggested that the dissociation of the peroxide ([BOND]O[BOND]O[BOND]) bonds of the copolyperoxide chain controlled the degradation process. Both the thermal stability and flexibility decreased with an increase in the indene units in the copolyperoxide.

    2. Living free-radical polymerization of styrene under a constant source of γ radiation (pages 19–25)

      John F. Quinn, Leonie Barner, Ezio Rizzardo and Thomas P. Davis

      Version of Record online: 6 NOV 2001 | DOI: 10.1002/pola.10086

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      60Co γ radiation was used with reversible addition–fragmentation chain transfer as a means of performing living polymerization of styrene. This development affords the grafting of narrow polydispersity, block, and star structures onto existing polymer surfaces as well as opens the door to a wealth of kinetic experiments using the constant radical flux generated by γ radiation.

    3. Kinetics of free-radical graft polymerization of 1-vinyl-2-pyrrolidone onto silica (pages 26–42)

      Van Nguyen, Wayne Yoshida, Jeng-Dung Jou and Yoram Cohen

      Version of Record online: 7 NOV 2001 | DOI: 10.1002/pola.10081

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      A kinetic model is proposed for the aqueous free-radical graft polymerization of 1-vinyl-2-pyrrolidone onto silica activated with vinyltrimethoxysilane. The graft polymerization, initiated with hydrogen peroxide, is studied over a temperature range of 70–90 °C, with the initial monomer concentration ranging from 10 to 40 vol%. The kinetic model is able to describe the experimental kinetic rate order, with respect to the monomer concentration, which ranges from 1 to about 3/2.

    4. Substituent effects on the polycondensation of quinones with aromatic amines to form poly(quinone imine)s (pages 43–54)

      James Dibattista, Brian M. Schmidt, Anne Buyle Padias and H. K. Hall Jr.

      Version of Record online: 7 NOV 2001 | DOI: 10.1002/pola.10089

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      The effect of alkyl and fluorine groups on the polycondensation of aromatic diamines and quinones to form poly(quinone imine)s was investigated. Alkyl substituents were harmful in the polycondensation of both anthraquinones and benzoquinones with aromatic diamines. Polymers of the difluoroanthraquinones with aromatic diamines were obtained in high yields, although not in high molecular weights, and no stereocontrol was found.

    5. Synthesis and characterization of poly(arylene ether)s derived from 4,4′-bishydroxybiphenyl and 4,4′-bishydroxyterphenyl (pages 55–69)

      Arun Kashinath Salunke, Mukesh Kumar Madhra, Mamta Sharma and Susanta Banerjee

      Version of Record online: 14 NOV 2001 | DOI: 10.1002/pola.10078

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      A series of poly(arylene ether)s were successfully prepared by aromatic, nucleophilic substitution reactions with various perfluoroalkyl-activated bisfluoromonomers with 4,4′-bishydroxybiphenyl and 4,4′-bishydroxyterphenyl. The products exhibited number-average molecular weights up to 69,300; very good thermal stability, up to 548 °C for 5% weight loss according to thermogravimetric analysis under synthetic air; and high glass-transition temperatures, up to 259 °C according to differential scanning calorimetry, depending on the exact repeat unit structure. These polymers were soluble in a wide range of organic solvents. Thin films of these poly(arylene ether)s exhibited tensile strengths up to 132 MPa, moduli up to 3.34 GPa, and elongations at break up to 84%, depending upon their exact repeating unit structures.

    6. Synthesis and characterization of novel aliphatic polycarbonates (pages 70–75)

      Xu-Li Wang, Ren-Xi Zhuo, Li-Jian Liu, Feng He and Gang Liu

      Version of Record online: 14 NOV 2001 | DOI: 10.1002/pola.10088

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      A novel six-membered cyclic carbonate monomer (5-benzyloxy-trimethylene carbonate) was synthesized starting from glycerol. It was ring-opening polymerized (ROP) to poly(5-benzyloxy-trimethylene carbonate) in bulk at 150 °C using aluminum isobutoxide, aluminum isopropoxide, or stannous octanoate as catalysts. The protecting benzyl groups were removed by hydrogenolysis to give the corresponding polycarbonate with pendant hydroxyl groups.

    7. Poly(ethylene terephthalate) copolymers containing 5-nitroisophthalic units. III. Methanolytic degradation (pages 76–87)

      Darwin P. R. Kint, Antxon Martínez de Ilarduya, Jordi J. Bou and Sebastián Muñoz-Guerra

      Version of Record online: 15 NOV 2001 | DOI: 10.1002/pola.10094

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      The comonomer bis(2-hydroxyethyl) 5-nitroisophthalate underwent methanol transesterification much faster than bis(2-hydroxyethyl) terephthalate. Accordingly, random poly(ethylene terephthalate) (PET) copolymers containing 10 and 30 mol % of 5-nitroisophthalic units (PETNI) degraded faster than PET. The methanolysis of the copolymers increased with the content of nitrated units and occurred preferentially in the amorphous phase.

    8. High-temperature elastomers from silarylene-siloxane-diacetylene linear polymers (pages 88–94)

      Craig L. Homrighausen and Teddy M. Keller

      Version of Record online: 15 NOV 2001 | DOI: 10.1002/pola.10091

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      The syntheses and characterization of linear silarylene-siloxane-diacetylene polymers 3a–c and their conversion to crosslinked elastomeric materials are discussed. The linear polymers were prepared via polycondensation of 1,4-bis(dimethylaminodimethylsilyl) butadiyne with disilanol prepolymers. Heat treatment of the linear polymers results in a crosslinking reaction between the diacetylene units and formation of elastomeric materials 4a–c.

    9. Chemical-surface modification of polymers using atmospheric pressure nonequilibrium plasmas and comparisons with vacuum plasmas (pages 95–109)

      M. J. Shenton, G. C. Stevens, N. P. Wright and X. Duan

      Version of Record online: 19 NOV 2001 | DOI: 10.1002/pola.10056

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      The atmospheric pressure nonequilibrium plasma were used to chemically modify the surfaces of polymers. Similarities and differences between atmospheric plasma and vacuum plasma-surface treatments are highlighted as well as the key features of both classes of plasmas. Surface oxidation, cleaning, and reduction were achievable by using a variety of atmospheric plasma-source gases on commodity polymers such as high-density polyethylene, low-density polyethylene, polypropylene, poly(ethylene terephthalate), and poly(methyl methacrylate). Data are reported to support these types of surface modifications from the analysis of atmospheric plasma-treated polymers by surface Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and contact-angle measurements. The importance of downstream processing and postexposure reactions is also discussed.

    10. Organosoluble and transparent polyimides derived from alicyclic dianhydride and aromatic diamines (pages 110–119)

      J. G. Liu, M. H. He, H. W. Zhou, Z. G. Qian, F. S. Wang and S. Y. Yang

      Version of Record online: 19 NOV 2001 | DOI: 10.1002/pola.10100

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      Organosoluble polyimides were synthesized with the alicyclic dianhydride 1,8-dimethylbicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMBD) and aromatic diamines. The polyimides possessed good solubility both in strong dipolar solvents and in common solvents and good thermal properties. Strong and flexible films of the polyimides, with the cutoff of ultraviolet–visible absorption lower than 310–320 nm, exhibited good features as the alignment layers for nematic liquid crystals with pretilt angles of 1.5–2.9°.

    11. Photoinitiated polymerization of methacrylic monomers in a poly(methyl methacrylate) matrix: A comparative study with other matrices (styrene–butadiene–styrene, polystyrene, and polybutadiene) (pages 120–127)

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

      Version of Record online: 19 NOV 2001 | DOI: 10.1002/pola.10099

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      The kinetics and mechanism of the photoinitiated polymerization of 1,6-hexanediol dimethacrylate (HDDMA) in a poly(methyl methacrylate) (PMMA) matrix were studied. For this system, a reaction-diffusion termination mechanism occurred from the start of the polymerization, and it was predominantly maintained until high monomer concentrations, probably because of the relatively high intermolecular attraction force between the PMMA matrix and HDDMA monomer. In addition, a comparative study of the photoinitiated polymerization of methacrylic monomers in four different polymeric matrices (styrene–butadiene–styrene, polystyrene, polybutadiene, and PMMA) was carried out.

    12. Copolymerization of propylene with higher α-olefins in the presence of the syndiospecific catalyst i-Pr(Cp)(9-Flu)ZrCl2/MAO (pages 128–140)

      Sven M. Graef, Udo M. Wahner, Albert J. Van Reenen, Robert Brüll, Ronald D. Sanderson and Harald Pasch

      Version of Record online: 19 NOV 2001 | DOI: 10.1002/pola.10093

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      Random syndiotactic copolymers of propylene with 1-hexene, 1-dodecene, and 1-octadecene were synthesized with i-Pr(Cp)(9-Flu)ZrCl2. The stereoregularity of the copolymers decreased because of an increase in skipped insertions in the presence of the higher 1-olefin. The melting temperature of the copolymers decreased linearly with increasing comonomer content independently of the comonomer nature. Crystallization analysis fractionation revealed a small but significant dependence of the crystallization temperature on the nature of the comonomer.

    13. Thermotropic liquid-crystalline polyesters of 4,4′-biphenol and phenyl-substituted 4,4′-biphenols with 4,4′-oxybisbenzoic acid (pages 141–155)

      Pradip K. Bhowmik, Haesook Han, James J. Cebe and Ronald A. Burchett

      Version of Record online: 19 NOV 2001 | DOI: 10.1002/pola.10097

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      A series of thermotropic polyesters based on 4,4′-biphenol, 3-phenyl-4,4′-biphenol, and 3,3′-bis(phenyl)-4,4′-biphenol, 4,4′-oxybisbenzoic acid, and other aromatic dicarboxylic acids were synthesized by melt polycondensation and examined for their thermotropic liquid-crystalline properties with a wide number of experimental techniques.

    14. Synthesis and characterization of biodegradable poly(ϵ-caprolactone urethane)s. I. Effect of the polyol molecular weight, catalyst, and chain extender on the molecular and physical characteristics (pages 156–170)

      Katarzyna Gorna, Stefan Polowinski and Sylwester Gogolewski

      Version of Record online: 20 NOV 2001 | DOI: 10.1002/pola.10096

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      Biodegradable polyurethanes with potential for applications in medical implants were synthesized with aliphatic hexamethylene and/or isophorone diisocyanate, poly(ϵ-caprolactone) diols, various chain extenders, and the catalysts stannous octoate, dibutyltin dilaurate, ferric acetyl acetonate, magnesium methoxide, zinc octoate, and manganese 2-ethyl hexanoate. The materials had the assumed chemical structures, polydispersity indices ranging from 1.5 to 1.9, and glass-transition temperatures ranging from −38 to −57 °C. The tensile strengths and tensile moduli of the materials were 12–63 and 8–107 MPa, respectively. The least effective catalyst was magnesium methoxide, and the most effective was ferric acetyl acetonate.

    15. Determination of the equilibrium constant for the reaction between bisphenol A and diphenyl carbonate (pages 171–178)

      Stephen M. Gross, W. Clayton Bunyard, Karen Erford, George W. Roberts, Douglas J. Kiserow and Joseph M. DeSimone

      Version of Record online: 20 NOV 2001 | DOI: 10.1002/pola.10098

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      Despite the industrial significance of poly(bisphenol A carbonate), there is a scarcity of open literature on the equilibrium of the melt-phase process. In fact, the equilibrium constant (Keq) for this reaction has never been measured directly. This article describes a process on the basis of NMR for the measurement of Keq for the reaction between bisphenol A and diphenyl carbonate in the presence and absence of a catalyst. The apparent enthalpy and entropy were calculated using a van't Hoff plot. Decomposition of bisphenol A is a common side reaction in the melt-phase reaction performed at high temperatures in the presence of catalyst. The effect of these side reactions on the Keq in the presence of catalyst is determined.

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