Journal of Polymer Science Part A: Polymer Chemistry

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

1 June 2001

Volume 39, Issue 11

Pages 1817–1954

  1. Articles

    1. Top of page
    2. Articles
    1. Syndiospecific polymerization of styrene catalyzed by CpTiCl2(OR) complexes (pages 1817–1824)

      Haiyan Ma, Yue Zhang, Bin Chen, Jiling Huang and Yanlong Qian

      Version of Record online: 5 APR 2001 | DOI: 10.1002/pola.1159

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      Five new CpTiCl2(OR) complexes, where R was methoxyethyl, methoxypropyl, methoxyisopropyl, o-methoxyphenyl, or tetrahydrofurfuryl, were synthesized and tested as catalyst precursors for the syndiospecific polymerization of styrene. The influence of alkoxyl ligands is discussed.

    2. Synthesis and characterization of new soluble polyamides derived from 2,6-bis(4-aminophenyl)-3,5-dimethyltetrahydro-4H-pyran-4-one (pages 1825–1832)

      José M. García, Félix García, Roberto Sanz, José G. de la Campa, Angel E. Lozano and Javier de Abajo

      Version of Record online: 5 APR 2001 | DOI: 10.1002/pola.1160

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      Polyamides were prepared from aromatic dicarboxylic acid chlorides and a new condensation monomer, 2,2-bis(aminophenyl)-3,5-dimethyltetrahydro-4H-pyran-4-one. The polymers were attained in high yields and high molecular weights, except for biphenyl-2,2′-dicarboxylic acid, which gave low molecular weight polyamides because of its lower reactivity. These novel polyamides were soluble in polar organic solvents and showed glass-transition temperatures greater than 260 °C, with initial decomposition temperatures (from thermogravimetric analysis) of about 350 °C. They were essentially amorphous and exhibited good film-forming properties.

    3. Synthesis and properties of polydimethylsiloxane-containing block copolymers via living radical polymerization (pages 1833–1842)

      Kim Huan, Laurence Bes, David M. Haddleton and Ezat Khoshdel

      Version of Record online: 6 APR 2001 | DOI: 10.1002/pola.1161

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      Polydimethylsiloxane (PDMS) block copolymers were synthesized by using PDMS macroinitiators with copper-mediated living radical polymerization.

    4. Synthesis and kinetics of polymerization of hydrophilic monomers: 2,3-dihydroxypropylacrylate and 2,3-dihydroxypropylmethacrylate (pages 1843–1853)

      F. García, J. L. de la Peña, J. J. Delgado, N. García, J. Guzmán, E. Riande and P. Calle

      Version of Record online: 10 APR 2001 | DOI: 10.1002/pola.1162

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      The reactions between acrylic and methacrylic chlorides and glycerol that fabricate five different compounds were theoretically and experimentally investigated. Very large differences were found between the seven rate constants that intervene in these reactions. The radical polymerization of 2,3-dihydroxypropylacrylate and 2,3-dihydroxypropylmethacrylate (GM) was studied, and the polymerization rates were determined by ultraviolet spectroscopy. The results were compared with those obtained in the same conditions for methyl acrylate, methyl methacrylate, 2-hydroxyethylacrylate, and 2-hydroxyethylmethacrylate. Electron paramagnetic resonance spectroscopy was also used to examine the polymerization of GM.

    5. Synthesis of novel phosphinic acid-containing polymers (pages 1854–1859)

      Kenji Miyatake and Allan S. Hay

      Version of Record online: 10 APR 2001 | DOI: 10.1002/pola.1163

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      Three arylene difluoride monomers containing phosphine oxide (1), phosphinic acid (2), or phosphinate ester (3) groups were prepared and polymerized with bisphenol A to give novel poly-(arylene ether)s (4, 5, and 6). The polymers obtained had moderate molecular weights (ηinh: 0.14–0.30 dL g−1 in N-methylpyrrolidinone) and glass-transition temperatures (Tg: 102–200°C), depending on the phosphine group in the main chain. Using bis(4-fluorophenyl)sulfone as a comonomer improved the polymerization to give copolymers with higher solution viscosities. The stoichiometric investigation revealed that 7 mol % excess of fluoride monomer gave the highest molecular weight copolymer 8 with ηinh of 0.78 dL g−1, which had a Tg of 176 °C, a Td10% of 432 °C, and formed a hard film by casting from solution.

    6. Terpolymerization monitoring with ATR-FTIR spectroscopy (pages 1860–1876)

      Hong Hua and Marc A. Dubé

      Version of Record online: 11 APR 2001 | DOI: 10.1002/pola.1164

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      Attenuated total relflection-Fourier transform infrared spectroscopy equipped with conduit and diamond-composite sensor technology was used to monitor butyl acrylate, methyl methacrylate, and vinyl acetate solution terpolymerizations off-line and emulsion terpolymerizations in-line. Monomer conversion and terpolymer composition changes as a function of time were calculated by monitoring the peak height of characteristic absorbances of each monomer. Results obtained from the ReactIR™ 1000 reaction-analysis system agreed well with those determined by traditional gravimetry and 1H NMR spectroscopy.

    7. Graft copolymerization induced by thermal reactions of the binary alkali salts of poly(carboxylic acid)–brominated carboxylic acid in bulk (pages 1877–1885)

      Yoshio Kasashima, Koichi Shinoda, Hiroshi Matsushima, Satoko Shitagaki, Mari Inoki, Fumihiko Akutsu, Tadashi Shimura and Masaomi Tsuchiya

      Version of Record online: 12 APR 2001 | DOI: 10.1002/pola.1165

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      Thermal reactions of binary alkali salts, such as sodium or potassium poly(4-vinylbenzoate)-2-bromopropanoate, in bulk resulted in graft copolymerization to yield a graft copolymer containing poly(4-vinylbenzoate) in the main chain and polylactic acid in the side chain.

    8. Homopolymerization and [2 + 4]/[3 + 2] cycloaddition in the reaction of nitroethylene with vinyl ethers (pages 1886–1891)

      Won-Suk Shin, Anne Buyle Padias and H. K. Hall, Jr.

      Version of Record online: 17 APR 2001 | DOI: 10.1002/pola.1166

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      In the reaction of nitroethylene and vinyl ethers, cycloaddition was accompanied by the anionic homopolymerization of nitroethylene. Mechanistically, the cycloadducts formed by a cis–syn concerted approach of the reactants, whereas a trans–anti approach gave a zwitterionic tetramethylene that initiated anionic homopolymerization.

    9. Vapor deposition polymerization of heteroatom-bridged [2.2]paracyclophanes: 1,9-dithia[2.2]paracyclophane and 1,9-dithia[2.2]paracyclophane-1,1,9,9-tetroxide (pages 1892–1900)

      Takahito Itoh, Shizuhiko Ohtake, Yukihiro Mitsuda and Masataka Kubo

      Version of Record online: 17 APR 2001 | DOI: 10.1002/pola.1167

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      1,9-Dithia[2.2]paracyclophane-1,1,9,9-tetroxide (3) was synthesized as white needles in a high yield from 1,9-dithia[2.2]paracyclophane (2) by oxidation with m-chloroperbenzoic acid, and its molecular structure was determined with single-crystal X-ray diffraction analysis. Vapor deposition polymerizations of 2 and 3 gave amorphous and brittle polymer films along with considerable amounts of nonpolymeric byproducts. A polymer film from 2 was a copolymer of p-(phenylene-methylenesulfide) with p-(phenylene-methylene) units, and a polymer film from 3 was a homopolymer of p-(phenylene-methylene) units. Plausible mechanisms for vapor deposition polymerization of both cyclophanes are proposed.

    10. Triisobutylaluminum as cocatalyst for zirconocenes. I. Sterically opened zirconocene/triisobutylaluminum/perfluorophenylborate as highly effective ternary catalytic system for synthesis of low molecular weight polyethylenes (pages 1901–1914)

      A. N. Panin, T. A. Sukhova and N. M. Bravaya

      Version of Record online: 18 APR 2001 | DOI: 10.1002/pola.1168

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      Ethylene polymerizations with Me2SiCp*NtBuZrX2 (Cp* = C5(CH3)4; X = Cl, Me) or Me2SiCp2ZrX2 (X = Cl, Me) with combined activator triisobutylaluminum/perfluorophenylborate CatB(C6F5)4 (Cat = CPh3, Me2NHPh) have been performed within a wide range of ethylene pressures, different Al/Zr ratios, and Zr/B = 1. High-molecular weight linear polyethylene is formed with dichlorides complexes, while low molecular weight branched polyethylene is generated with dimethylated zirconocenes.

    11. Triisobutylaluminum as cocatalyst for zirconocenes. II. Triisobutylaluminum as a component of a cocatalyst system and as an effective cocatalyst for olefin polymerization derived from dimethylated zirconocenes (pages 1915–1930)

      A. N. Panin, Z. M. Dzhabieva, P. M. Nedorezova, V. I. Tsvetkova, S. L. Saratovskikh, O. N. Babkina and N. M. Bravaya

      Version of Record online: 18 APR 2001 | DOI: 10.1002/pola.1169

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      Investigation of the catalytic behavior of dimethylated zirconocenes: Me2SiCp*NtBuZrMe2, Me2SiCp2ZrMe2, Cp2ZrMe2, Ind2ZrMe2, Me2SiInd2ZrMe2, Et(2-MeInd)2ZrMe2, Me2Si(2-MeInd)2ZrMe2 with the combined activator TIBA/CPh3B(C6F5)4 (Al/Zr = 250; B/Zr = 1) in ethylene polymerization at increased monomer pressures (5–11 bar, 30 °C) has been carried out. It has been shown that the zirconocenes bearing substituent at the 2-position of the indenyl ring may be well activated with TIBA alone yielding active species effective in ethylene and propylene polymerization.

    12. Enzyme-catalyzed transesterification of vinyl esters on cellulose solids (pages 1931–1939)

      Jiangbing Xie and You-Lo Hsieh

      Version of Record online: 18 APR 2001 | DOI: 10.1002/pola.1170

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      The enzyme-catalyzed transesterification of cellulose solids in organic media have been demonstrated. Subtilisin Carsberg was found to be catalytically active in the transesterification of cellulose with vinyl propionate and vinyl acrylate in anhydrous pyridine. The regioselectivity of these transesterification reactions was confirmed by reactions on specifically substituted cellulose derivatives. The cellulose esters from enzyme-catalyzed transesterification could be hydrolyzed partially by the same enzyme in aqueous media. Surface grafting of cellulose acrylate was demonstrated using the azobisisobutyronitrile-initiated polymerization of acrylonitrile in dimethylformamide.

    13. Synthesis and polymerization of functionalized dendritic macromonomers (pages 1940–1954)

      Serge Vetter, Sabine Koch and A. Dieter Schlüter

      Version of Record online: 19 APR 2001 | DOI: 10.1002/pola.1171

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      The synthesis of dendritic building blocks (dendrons) of the first generation (G1) and the second generation, which carry differently protected amine groups in the periphery, is reported. The dendrons are used for the synthesis of the corresponding acrylic and methacrylic macromonomers. Their polymerization behavior under radical conditions is investigated. The G1 dendronized polymers are decorated at their peripheral amino groups, that is, with the chiral amino acid L-phenylalanine by the attach-to approach.