Journal of Polymer Science Part A: Polymer Chemistry

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

15 June 2005

Volume 43, Issue 12

Pages 2451–2678, 2606 –2624

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      Structural defects in poly(vinyl chloride) (pages 2451–2467)

      William H. Starnes Jr.

      Version of Record online: 3 MAY 2005 | DOI: 10.1002/pola.20811

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      The anomalous structures in poly(vinyl chloride) have been identified and quantified, and their mechanisms of formation have been established. Depicted here is the process that not only produces the thermally labile internal allylic (IA) segment but also serves as one of the mechanisms for chain transfer to the monomer during the polymerization of vinyl chloride (VC).

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    1. Preparation of poly(propylene-co-γ-butyrolactone carbonate) and release profiles of drug-loaded microcapsules (pages 2468–2475)

      Lingbin Lu and Kelong Huang

      Version of Record online: 26 APR 2005 | DOI: 10.1002/pola.20719

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      A new aliphatic poly(propylene-co-γ-butyrolactone carbonate) (PPCG) was successfully synthesized by copolymerization of carbon dioxide, propylene oxide (PO), and γ-butyrolactone (GBL). GBL was inserted into the backbone of poly(propylene carbonate) (PPC). PPCG had stronger degradability than PPC in pH 7.4 PBS. PPCG and PPC microcapsules were prepared by the water-in-oil-in-water type multiple emulsions method. The PPCG microcapsules, about 2 μm in diameter, had smooth and spherical surfaces. The glucose release test revealed that the glucose release speed of the PPCG–glucose microcapsules was more than eight times faster than that of the PPC–glucose microcapsules in pH 7.4 PBS.

    2. Synthesis, characterization, and properties of polysilaethers containing moiety Si[BOND]H bonds in the side chain (pages 2476–2482)

      Mengzhong Cui, Zhuyun Li, Jingyu Xi, Sixun Zheng and Xiaozhen Tang

      Version of Record online: 5 MAY 2005 | DOI: 10.1002/pola.20710

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      A synthetic route to polysilaethers containing moiety Si[BOND]H bonds in the side chain is reported which allows access to hitherto inaccessible oxygen-interrupt polysilanes. By Wurtz reductive coupling reaction, an equimolar ratio of dichloromethylsilane and alkali metal yields monomodal polysilaethers. The stretching vibration bands of Si-H bond were obviously split into two components at 2169 cm−1 and 2100 cm−1, respectively. The synthetic polymer presents the UV absorption and photoluminescence which is due to the interactions of the σ(Si[BOND]Si) orbital electron delocalization and the pπ(O)–σ*π(Si[BOND]O) delocalization along the (SiSiO)n skeleton.

    3. Octa(maleimido phenyl) silsesquioxane copolymers (pages 2483–2494)

      P. Santhana Gopala Krishnan and Chaobin He

      Version of Record online: 5 MAY 2005 | DOI: 10.1002/pola.20720

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      Octa(maleimido phenyl) silsesquioxane (OMPS) was successfully synthesized and characterized by FT-IR, NMR, GPC, and WAXD. OMPS was copolymerized with varying molar percents of N,N′-p-phenylenedimaleimide and urethane methacrylate macromonomer by thermal and free-radical polymerization, respectively. Copolymers were characterized by DSC, DEA, TGA, and WAXD.

    4. Acrylamide inverse microemulsion polymerization in a paraffinic solvent: Rolling-M-245 (pages 2495–2503)

      M. Rentería, M. Muñoz, J. R. Ochoa, L. C. Cesteros and I. Katime

      Version of Record online: 6 MAY 2005 | DOI: 10.1002/pola.20721

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      Pseudoternary phase diagrams have been made, for four different hydrophilic-lipophilic balance (HLB) values at 25 °C, of an acrylamide–oil–surfactant ternary system. The curves show the transition between a turbid emulsion and an optical transparent microemulsion. The range of compositions for a stable microemulsion is a strong function of HLB in this system.

    5. Modification of photoinitiated cationic epoxide polymerizations by sulfides (pages 2504–2519)

      B. Falk, M. R. Zonca Jr. and J. V. Crivello

      Version of Record online: 9 MAY 2005 | DOI: 10.1002/pola.20726

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      The addition of sulfides has a marked effect on the rates of onium salt induced photoinitiated cationic ring-opening polymerizations of epoxide monomers. Dialkyl sulfides strongly inhibit the photopolymerizations of these monomers, whereas diaryl sulfides have a retarding effect on the photopolymerizations. A mechanism is proposed that involves the formation of sulfonium salts as intermediates.

    6. Dependence of the luminescent properties and chain length of poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] on the formation of cis-vinylene bonds during Gilch polymerization (pages 2520–2526)

      Yang-Liang Fan and King-Fu Lin

      Version of Record online: 6 MAY 2005 | DOI: 10.1002/pola.20717

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      The coil nature imposed by cis-vinylene bonds formed during the Gilch polymerization of poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] strongly inhibits the growth of polymer chains and renders a blueshift of the photoluminescence spectrum.

    7. Synthesis of a highly transparent poly(o-hydroxyamide) in the i-line region and its application to photosensitive polymers (pages 2527–2535)

      Fumihiro Toyokawa, Ken-Ichi Fukukawa, Yuji Shibasaki, Shinji Ando and Mitsuru Ueda

      Version of Record online: 6 MAY 2005 | DOI: 10.1002/pola.20729

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      A novel poly(σ-hydroxyamide) (PHA) based photosensitive polymer that exhibits high transparency at 365 nm wavelength (i-line) has been developed. Time-dependent density functional theory calculations using the B3LYP hybrid functional were performed to predict the transparencies of various hydroxyamides in the i-line region. Based on that, 4,4′-sulfonylbis(o-aminophenol) was polymerized with 4,4′-oxybis(benzoyl chloride), and the resulting PHA (PHA-S) showed a high transparency. Finally, positive-type photosensitive PHA-S with a crosslinker 1,3,5-tris[(2-vinyloxy)ethoxy]benzene and a photoacid generator (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-2-(methylphenyl)acetonitrile showed photosensitivity of 14 mJ cm−2 and contrast of 2.7 at 1.5-μm film. A 4.5-μm resist film provided 10 μm line-and-space resolution by i-line irradiation.

    8. Chain-end modification of living anionic polybutadiene with diphenylethylenes and styrenes (pages 2536–2545)

      Ellen H. D. Donkers, Robin X. E. Willemse and Bert Klumperman

      Version of Record online: 6 MAY 2005 | DOI: 10.1002/pola.20725

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      Three different modification reactions at the chain end of poly(butadienyl)lithium have been investigated. In all cases, the influence of a Lewis base on the progress of the reaction has been examined. The first modification reaction with α-methylstyrene leads to partial functionalization and oligomerization. The second reaction with 1,2-diphenylethylenes results in monoaddition to the poly(butadienyl)-lithium chain ends. Quantitative functionalization is not obtained. In the third modification reaction, a small polystyrene block is successfully added to the chain ends, as shown by a detailed matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis. Nearly quantitative block copolymer formation is achieved, with an average styrene block size of four monomer units and a polydispersity index of 1.19 for the polystyrene block.

    9. Continuous precipitation polymerization of acrylic acid in supercritical carbon dioxide: The polymerization rate and the polymer molecular weight (pages 2546–2555)

      Tao Liu, Joseph M. DeSimone and George W. Roberts

      Version of Record online: 6 MAY 2005 | DOI: 10.1002/pola.20728

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      The precipitation polymerization of acrylic acid in supercritical carbon dioxide was studied in a continuous stirred tank reactor with 2,2′-azobis(2,4-dimethyl-valeronitrile) as the free-radical initiator. The reactor temperature was between 50 and 90 8C, the pressure was 207 bar, and the average residence time was between 12 and 40 min. The product polymer was a white, dry, fine powder that dissolved in water. A wide range of polymer molecular weights (5-200 kg/mol) could be obtained. The observed kinetics suggest that polymerization reactions took place in both the supercritical fluid and the precipitated polymer particles.

    10. Selective retention of some polyaromatic hydrocarbons by highly crosslinked polymer networks (pages 2556–2566)

      Ken Hosoya, Hiroshi Aoki, Takuya Kubo, Masashi Teramachi, Nobuo Tanaka and Jun Haginaka

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20730

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      Highly crosslinked polymer networks were characterized in terms of structural differences based on the crosslinked network structures with their chromatographic molecular retentivity for some polyaromatic hydrocarbons (PAHs). Because PAHs were utilized in the chromatographic characterization, tiny differences of the crosslinked polymer networks were found to be observed in terms of chromatographic molecular retentivity. Ethylene glycol dimethacrylate afforded molecular retentivity for anthracene, and this recognition ability was changed among the polymerization time. In addition, 1,4-butandiol dimethacrylate afforded the molecular retentivity to pyrene.

    11. N-Bromosuccinimide as a thermal iniferter for radical polymerization (pages 2567–2573)

      Hong Zhou, Jianguo Jiang and Keda Zhang

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20745

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      N-Bromosuccinimide (NBS) was used as a thermal iniferter for the initiation of the bulk polymerizations of methyl methacrylate, methyl acrylate, and styrene. The polymerizations showed the characteristics of a living polymerization: both the yields and the molecular weights of the resultant polymers increased linearly as the reaction time increased. The molecular weight distributions of the polymers were 1.42–1.95 under the studied conditions. The resultant polymers could be used as macroiniferters to reinitiate the polymerization of the second monomer. The copolymers poly(methyl methacrylate)-b-polystyrene and polystyrene-b-poly(methyl methacrylate) were obtained and characterized. End-group analysis of the resultant poly(methyl methacrylate), poly(methyl acrylate), and polystyrene confirmed that NBS behaved as a thermal iniferter.

    12. Synthesis and modeling of new phosphorus-containing acrylates (pages 2574–2583)

      Seyhan Salman, Aylin Ziylan Albayrak, Duygu Avci and Viktorya Aviyente

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20733

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      New phosphonic acid containing methacrylate monomers were synthesized through the reaction of t-butyl α-bromomethyl acrylate with triethyl phosphite followed by the selective hydrolysis of the phosphonate or t-butyl ester groups with trimethylsilyl bromide and trifluoroacetic acid. The copolymerization of these monomers with 2-hydroxyethylmethacrylate was investigated with photodifferential scanning calorimetry. Quantum mechanical tools were also used to understand the mechanistic behavior of the polymerization reactions of these synthesized monomers. The propagation and termination by chain-transfer reactions were considered and rationalized. A strong effect of the monomer structure on the rate of polymerization was observed.

    13. Pressure and trimethylaluminum effects on ethene/1-hexene copolymerization with methylaluminoxane-activated (1,2,4-Me3Cp)2ZrCl2: Trimethylaluminum suppression of standard termination reactions after 1-hexene insertion (pages 2584–2597)

      Ingvild Bruaseth, Matthias Bahr, Dirk Gerhard and Erling Rytter

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20632

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      Ethene homo- and copolymerizations with 1-hexene were catalyzed by methylaluminoxane (MAO)-activated (1,2,4-Me3Cp)2ZrCl2. Investigations on the effects of varying pressure and different concentrations of trimethylaluminum (TMA) have been performed. The characteristics of the copolymers are in accordance with expectations for changes in the ethene concentration: the incorporation of 1-hexene decreases whereas the melting point and crystallinity increase with increasing pressure. Copolymerizations with different additions of TMA, keeping the other polymerization conditions constant, show that the catalytic productivity, the 1-hexene incorporation, and the molecular weight are independent of the TMA concentration. The vinylidene content, however, decreases almost linearly with increasing TMA concentration.

    14. Long-term stability of an ambient self-curable latex based on colloidal dispersions in water of two reactive polymers (pages 2598–2605)

      Xiaonong Chen, Robert Pelton and Eli Ruckenstein

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20731

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      An ambient self-curable latex (ASCL) was prepared via the blending of a reactive chloride-functionalized polymer dispersion in water with a reactive tertiary amino-functionalized polymer dispersion in water. Upon casting and drying under ambient conditions, the ASCL could generate a crosslinked continuous polymer film. The crosslinkking occurred via the Menschutkin reaction (quaternization) between the two types of functional groups. Because this reaction was reversible at high temperatures, the film could be decrosslinked and hence was self-curable. The ASCL exhibited excellent colloidal and chemical stability during storage: no significant changes in the colloidal properties and crosslinking reactivity were observed after 48 months of storage.

    15. Preparation and characterization of waterborne poly(urethane urea) with well-defined hard segments (pages 2606 –2614)

      Dong Ya Yang, Chun Pu Hu and Sheng Kang Ying

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20732

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      A well-defined model hard segment was synthesized with 4,4′-diphenylmethane diisocyanate, dimethylolpropionic acid, and 1,4-butanediol by means of fractional steps. A series of polyester based polyurethaneurea (PUU) aqueous dispersions with this well-defined hard segment were prepared. These anionic type PUU aqueous dispersions have good dispersity in water and are stable at ambient temperature for more than one year. The films prepared with the PUU aqueous dispersions exhibit the excellent water resistance, i.e. low equilibrium water absorbing capacity, and high contact angle of water on the surface of the films.

    16. Synthesis and swelling behavior of comb-type grafted hydrogels by reversible addition–fragmentation chain transfer polymerization (pages 2615 –2624)

      Qunfeng Liu, Ping Zhang and Mangeng Lu

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20750

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      The comb-type grafted hydrogels poly(N-isopropylacrylamide)-g-poly(N-isopropyla crylamide) lpar;PNIPAM-g-PNIPAM) and poly(acrylic acid)-g-poly(N-isopropylacrylamide) (PAAc-g-PNIPAM) were prepared by reversible addition–fragmentation chain transfer polymerization. A macromolecular chain-transfer agent was prepared first. Then, hydrogels were obtained by a reaction with a comonomer (N-isopropylacrylamide or acrylic acid) in the presence of N,N-methylenebisacrylamide as a crosslinker. The equilibrium swelling ratios and the swelling and deswelling kinetics of PNIPAM-g-PNIPAM were measured. The effects of the chain length and amount on the swelling behavior were investigated. The deswelling mechanism was illustrated. Meanwhile, the PAAc-g-PNIPAM hydrogel was used to confirm the versatility of this novel method. It was prepared in an alcoholic medium, whereas hydrogen-bonding complexes formed in 1,4-dioxane, which was chosen as the reaction medium for the PNIPAM-g-PNIPAM hydrogel.

    17. Novel catalyst system of MCl2/FeCl3·6H2O/PPh3 (M = Ni, Co, or Mn) for the atom transfer radical polymerization of methyl methacrylate (pages 2625–2631)

      Cao Jian, Jin Chen and Keda Zhang

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20736

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      MCl2 (M = Ni, Co, Sn, or Mn) and PPh3 together acted as a catalyst for the radical polymerization of methyl methacrylate (MMA) in the presence of ethyl 2-bromoisobutyrate as an initiator. The four systems all led to conventional radical polymerizations, which yielded polymers with a weight-average molecular weight/number-average molecular weight (Mw/Mn) ratio greater than 2.0 and became well controlled when a certain amount of FeCl3·6H2O was added. The polymerizations of MMA catalyzed by these four FeCl3-modified catalyst systems provided well-defined polymers with low polydispersities (Mw/Mn < 1.28).

    18. Reversible addition–fragmentation chain transfer polymerization of 2-naphthyl acrylate with 2-cyanoprop-2-yl 1-dithionaphthalate as a chain-transfer agent (pages 2632–2642)

      Wei Zhang, Xiulin Zhu, Di Zhou, Xiaoyan Wang and Jian Zhu

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20746

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      Well-defined poly(2-naphthyl acrylate) (P2NA) was synthesized by reversible addition–fragmentation chain transfer polymerization. P2NA showed a strong ultraviolet absorption at 270 nm (ϵ, UV absorbance intensity = 2.11 × 104 M−1 cm−1) and had a high fluorescence intensity that increased as follows: ethyl acetate ≈ CH2Cl2 < CHCl3. Furthermore, the fluorescence intensity of P2NA increased as the molecular weight increased and was higher than that of 2-naphthyl acrylate; the fluorescence intensity of a poly(2-naphthyl acrylate)-b-polystyrene diblock polymer was higher than that of the original P2NA with the same concentration of naphthalene moieties.

    19. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry study on copolymers obtained by the alternating copolymerization of bis(γ-lactone) and epoxide with potassium tert-butoxide (pages 2643–2649)

      Chenxi Zhang, Bungo Ochiai and Takeshi Endo

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20749

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      Polymer samples obtained by the anionic copolymerization of a bis(γ-lactone), 2,8-dioxa-1-methylbicyclo[3.3.0]octane-3,7-dione (1), and glycidyl phenyl ether (2) with potassium tert-butoxide have been analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy. This study has revealed the mechanism of this copolymerization and the side reactions, which are suppressed efficiently by copolymerization with an excess of 1.

    20. Novel polystyrene-supported zirconocene catalyst for olefin polymerization and its catalytic kinetics (pages 2650–2656)

      Wenqin Wang, Li Wang, Jianfeng Wang, Jianjun Wang and Zhenli Ma

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20676

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      Through the Diels–Alder reaction between cyclopentadiene groups attached on polystyrene, a reversibly crosslinked network was formed. The metallocene was supported into the network without a chemical bond to network. The reversibly crosslinked network of polystyrene fragmented during olefin polymerization. As a result of the network fragmentation, the catalyst showed high and stable olefin polymerization activity.

    21. Synthesis and characterization of fluorene end-labeled polystyrene with atom transfer radical polymerization (pages 2657–2665)

      Caton C. Goodman, Amanda C. Roof, Eric S. Tillman, Bellamarie Ludwig, Dougie Chon and Michael I. Weigley

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20760

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      Fluorene end-labeled polystyrene was prepared by atom transfer radical polymerization with 9-bromofluorene as the initiator. Reactions were carried out in bulk or tetrahydrofuran solutions at temperatures of 80 °C or above. Analysis by gel permeation chromatography indicated that the polymers formed had low polydispersities with molecular weights consistently 2–5 times higher than calculated based on monomer-to-initiator ratios. Coupling of two fluorenyl radicals, formed by activation of the 9-bromofluorene (shown as kt, the rate termination), was found to compete with initiation, leading to the higher-than-expected molecular weight values while giving rise to a fluorene dimer. The polymerization, once began, was found to proceed in a living fashion (shown as kp, the rate of polymerization). UV–vis spectrometry indicated near-quantitative fluorene labeling of the polystyrene.

    22. Copolymers of 2,5-bis[(4-methoxyphenyl) oxycarbonyl]styrene with styrene and methyl methacrylate: Synthesis, monomer reactivity ratios, thermal properties, and liquid crystalline behavior (pages 2666–2674)

      Yong-feng Zhao, Yi Yi, Xinghe Fan, Xiaofang Chen, Xinhua Wan and Qi-Feng Zhou

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20742

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      Copolymers of a liquid crystalline monomer, 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS), with St and MMA were prepared by free radical polymerization at low conversion in chlorobenzene with 2,2′-azobisisobutyronitrile (AIBN) as initiator. The reactivity ratios of the monomers were determined using the extended Kelen–Tudos (EKT) method. Structural parameters of the copolymers were obtained from possibility statistics and monomer reactivity ratios. The influence of the content of MPCS in copolymers on the glass transition temperature of the copolymers was investigated by an application of DSC. The thermogravimetric analysis of the copolymers revealed that the thermal stabilities of the two copolymer systems increased with an increase of the molar fraction of MPCS in the copolymers. The liquid crystalline behavior of the copolymer was also studied using DSC and POM. The results revealed that the copolymers with high MPCS molar contents could form liquid crystalline phases.

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    1. Determination of the extent of incorporation of a reactive surfactant in polystyrene latex particles via GPC (pages 2675–2678)

      Zhen Lai, E. David Sudol, Victoria L. Dimonie and Mohamed S. El-Aasser

      Version of Record online: 10 MAY 2005 | DOI: 10.1002/pola.20738

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      The reactive surfactant HITENOL BC20 (polyoxyethylene alkylphenyl ether ammonium sulfate containing 20 units of ethylene oxide) was used in emulsion polymerizations of styrene with potassium persulfate as initiator. A new method to determine the amount of chemically bound surfactant was developed using GPC combined with UV detection as shown in the figure. Comparing this GPC method with the serum replacement/FTIR method reveals it to be a relatively simple and more effective means of characterization.