Journal of Polymer Science Part A: Polymer Chemistry

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

1 July 2003

Volume 41, Issue 13

Pages 1871–2131

  1. Articles

    1. Top of page
    2. Articles
    3. Articles
    1. Densely grafted polyisocyanides synthesized by two types of polymerization techniques (pages 1871–1880)

      Yanqing Tian, Yi Li and Tomokazu Iyoda

      Article first published online: 9 MAY 2003 | DOI: 10.1002/pola.10741

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      A series of novel polyisocyanide-graft-polystyrenes and polyisocyanide-graft-[polystyrene-block-poly(butyl acrylate)]s were synthesized through both grafting-through and grafting-from routes with two types of living polymerization techniques: polymerization with the Pd–Pt μ-ethynediyl dinuclear complex as the initiator and catalyst for the polyisocyanide backbone and atom transfer radical polymerization for the grafted side chain.

    2. Supramolecular discotic liquid crystals from wedge-shaped diacetylenes and their polymerization (pages 1881–1891)

      In Ho Hwang, Seung Ju Lee and Ji Young Chang

      Article first published online: 9 MAY 2003 | DOI: 10.1002/pola.10736

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      Wedge-shaped diacetylenic compounds with an acetamide group at the focal point were organized into discotic liquid crystals by self-assembly, via hydrogen bonding. Their polymerization with UV irradiation yielded polymers with columnar structures.

    3. Synthesis of liquid crystalline–amorphous block copolymers by the combination of atom transfer and photoinduced radical polymerization mechanisms (pages 1892–1903)

      I. E. Serhatli, T. Kacar and A. Önen

      Article first published online: 9 MAY 2003 | DOI: 10.1002/pola.10732

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      The synthesis of ABA-type block copolymers, involving liquid-crystalline 6-(4-cyanobiphenyl-4′-oxy)hexyl acrylate (LC6) and styrene (St) monomer with copper-based atom transfer radical polymerization (ATRP) and photoinduced radical polymerization (PIRP), was studied. First, photoactive α-methylol benzoin methyl ether was esterified with 2-bromopropionyl bromide, and it was subsequently used for ATRP of LC6 in diphenylether in conjunction with CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine as a catalyst. The obtained photoactive functional liquid-crystalline polymer, poly[6-(4-cyanobiphenyl-4′-oxy)hexyl acrylate] (PLC6), was used as an initiator in PIRP of St. Similarly, photoactive polystyrenes were also synthesized and employed for the block copolymerization of LC6 in the second stage. The spectral, thermal, and optical measurements confirmed a full combination of ATRP and PIRP, which resulted in the formation of ABA-type block copolymers with very narrow polydispersities.

    4. Complexation of linear and poly(ethylene oxide)-grafted poly(methacryl oxyethyl trimethylammonium chloride) with poly(ethylene oxide-block-sodium methacrylate) (pages 1904–1914)

      Toni Andersson, Susanna Holappa, Vladimir Aseyev and Heikki Tenhu

      Article first published online: 9 MAY 2003 | DOI: 10.1002/pola.10742

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      The interactions between oppositely charged polyelectrolytes were studied in saline aqueous solutions as functions of the temperature and the salt and polymer concentrations. The polyanion was a diblock copolymer composed of a poly(ethylene oxide) block and a poly(sodium methacrylate) block. Two polycations were used, the homopolymer poly(methacryl oxyethyl trimethylammonium chloride) and its poly(ethylene oxide)-grafted analogue. By dynamic light scattering and turbidity measurements, it was observed that the salt concentration, temperature, and counterion size had a significant effect on the formation of the polymer complexes in aqueous solutions.

    5. Sulfuration and reversion reactions of brominated poly(isobutylene-co-isoprene) (pages 1915–1926)

      J. Scott Parent, Greg D. F. White, Darren J. Thom, Ralph A. Whitney and William Hopkins

      Article first published online: 14 MAY 2003 | DOI: 10.1002/pola.10744

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      The sulfuration and reversion chemistry of the allylic halide functionality within brominated poly(isobutylene-co-isoprene) was revealed by an analysis of the polymer as well as NMR and mass spectrometry characterizations of an appropriate model compound. Allylic polysulfides of various ranks were the primary vulcanization products, and they were susceptible to rapid oxidative reversion into thiophenes and subsequent reductive cure reversion into unsubstituted olefin.

    6. Preparation and characterization of highly polar polymeric sorbents from styrene–divinylbenzene and vinylpyridine–divinylbenzene for the solid-phase extraction of polar organic pollutants (pages 1927–1933)

      Núria Fontanals, Rosa Maria Marcé, Marina Galià and Francesc Borrull

      Article first published online: 14 MAY 2003 | DOI: 10.1002/pola.10743

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      This article explores the synthesis of styrene–divinylbenzene resins with different surface areas and the influence of these surface areas on their performance in the solid-phase extraction of polar compounds from water samples. As expected, increasing the surface areas increases the retention capability of polar compounds. To improve the retention properties, 4-vinylpyridine instead of styrene has been used in the polymerization and it has been found that a compromise is required between the percentage of 4-vinylpyridine, which increases the polarity of the sorbent, and the percentage of divinylbenzene, which increases the surface area.

    7. Strontium-based initiator system for ring-opening polymerization of cyclic esters (pages 1934–1941)

      Zhaohui Tang, Xuesi Chen, Qizhi Liang, Xinchao Bian, Lixin Yang, Longhai Piao and Xiabin Jing

      Article first published online: 12 MAY 2003 | DOI: 10.1002/pola.10740

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      An amino isopropoxyl strontium initiator with effective initiating activity for the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) and L-lactide (LLA) under mild conditions was prepared. It can adjust the molecular weight by the ratio of monomer to initiator. The block copolymer poly[ε-caprolactone-block-poly(L-lactide)] can be prepared by sequential polymerization of ε-CL and LLA. 1H NMR and Fourier transform infrared spectroscopy indicated the ROP of cyclic esters followed a coordination-insertion mechanism, and cyclic esters exclusively inserted into the Sr–O bond.

    8. Synthesis, characterization, and biological activity of N-(4-acetylphenyl)maleimide and its oxime, carbazone, thiosemicarbazone derivatives and their polymers (pages 1942–1951)

      Cengiz Soykan and İbrahim Erol

      Article first published online: 14 MAY 2003 | DOI: 10.1002/pola.10738

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      A new type of maleimide monomer, N-(4-acetylphenyl)maleimide (NAPMI), was synthesized. The oxime, carbazone, and thiosemicarbazone derivatives of NAPMI were prepared with hydroxylamine hydrochloride, semicarbazide hydrochloride, and thiosemicarbazide hydrochloride, respectively. Radical homopolymerization of NAPMI and its derivatives were prepared at 60 °C in dimethyl sulfoxide solution with azobisisobutyronitrile as an initiator. The monomers and their homopolymers were characterized with Fourier transform infrared and NMR techniques. The glass-transition temperatures, thermal stability, and ultraviolet stability of the polymers are compared. The activation energies of the thermal degradation of polymers were calculated by the Kissinger method. The antibacterial and antifungal effects of the monomers and polymers were also investigated on various bacteria and fungi.

    9. Synthesis of polyesters with pendant oxetane groups by the chemoselective alternating copolymerization of 3-ethyl-3-(glycidyloxymethyl)oxetane with carboxylic anhydride and its photochemical reaction (pages 1952–1961)

      Hiroto Kudo, Kensuke Ueda, Naotaka Sano and Tadatomi Nishikubo

      Article first published online: 16 MAY 2003 | DOI: 10.1002/pola.10734

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      The synthesis of polyesters with pendant oxetane groups by the chemoselective alternating copolymerization of 3-ethyl-3-(glycidyloxymethyl)oxetane (EGMO) with carboxylic anhydride and the photochemical reaction of the resulting polymer was examined. The alternating copolymerization of the oxirane moiety of EGMO with phthalic anhydride(PAn) proceeded chemoselectively with quaternary onium salts under appropriate reaction conditions, affording polymers with pendant oxetane groups with number-average molecular weights of 4700–7200 in 72–87% yields. Furthermore, the photocrosslinking reaction of the pendant oxetane groups of the resulting polymers proceeded smoothly with certain photoacid generators in the film state upon UV irradiation and yielded insoluble polymers.

    1. Anionic polymerization of methyl methacrylate initiated with late transition-metal halides/organolithium/triisobutylaluminum systems (pages 1962–1977)

      Eiji Ihara, Tsuyoshi Todaka and Kenzo Inoue

      Article first published online: 19 MAY 2003 | DOI: 10.1002/pola.10737

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      Anionic polymerization of methyl methacrylate (MMA) initiated with late transition-metal halide [manganese chloride (MnCl2), iron dichloride (FeCl2), iron trichloride (FeCl3), cobalt chloride (CoCl2), or nickel bromide (NiBr2)]/organolithium [nButyllithium (nBuLi) or phenyllithium (PhLi)]/triisobutylaluminum (iBu3Al) systems is described. Except for the system with NiBr2, the polymerizations of MMA afforded narrow molecular weight distribution poly(methyl methacrylate)s with high molecular weights in quantitative yields at 0 °C in toluene.

  2. Articles

    1. Top of page
    2. Articles
    3. Articles
    1. New aliphatic poly(ester-carbonates) based on 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one (pages 1978–1991)

      Brian D. Mullen, Chau N. Tang and Robson F. Storey

      Article first published online: 16 MAY 2003 | DOI: 10.1002/pola.10724

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      An allyl ester-containing carbonate 5-methyl-5-allyoxycarbonyl-1,3-dioxan-2-one (MAC) was synthesized in five steps from 2,2-bis(hydroxymethyl)propionic acid. Rac-LA copolymerized well with MAC, but CL copolymerizations produced insoluble products. Oligomeric macroinitiators of MAC and rac-LA were synthesized from stannous ethoxide and used for the controlled ring-opening polymerization of rac-LA. The polymerization kinetics were examined by monitoring the disappearance of the characteristic C[BOND]O ring stretch of the monomer at 1240 cm−1 with real-time in situ Fourier transform infrared spectroscopy. The unsaturated bonds of the MAC-functionalized polymers were expoxidized. NMR was used for microstructure identification of the polymers, and size exclusion chromatography and differential scanning calorimetry were used to characterize the new functionalized poly(ester-carbonates).

    2. Assembly of amphiphilic poly[2-(methacryloyloxy)ethyl phosphorylcholine] with cholesteryl moieties as terminal groups (pages 1992–2000)

      Kazuo Sugiyama, Kohei Shiraishi and Takako Matsumoto

      Article first published online: 16 MAY 2003 | DOI: 10.1002/pola.10746

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      Poly[2-(methacryloyloxy)ethyl phosphorylcholine]s (PMPCs) with one pendant cholesteryl moiety at the polymer end (PMPC-Chol-I and PMPC-Chol-II) and two pendant cholesteryl moieties at both polymer ends as terminal groups (PMPC-2Chol-I and PMPC-2Chol-II) were prepared. PMPC-Chol and PMPC-2Chol formed molecular assemblies in water. The blood compatibility of PMPC-2Chol was evaluated. A mixture of PMPC-2Chol-II and cholesterol as a drug model formed a lamellar type of complex.

    3. Synthesis and characterization of novel fluorinated polyimides based on 2,7-bis(4-amino-2-trifluoromethylphenoxy)naphthalene (pages 2001–2018)

      Sheng-Huei Hsiao, Chin-Ping Yang and Cheng-Lin Chung

      Article first published online: 15 MAY 2003 | DOI: 10.1002/pola.10748

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      A series of novel fluorinated polyimides were prepared from 2,7-bis(4-amino-2-trifluoromethylphenoxy)naphthalene and aromatic dianhydrides. These polyimides were characterized by high solubility, good film-forming ability, high optical transparency, excellent thermal stability, and good mechanical properties together with low dielectric constants.

    4. Reverse atom transfer radical polymerization of methyl methacrylate initiated by p-chlorobenzenediazonium tetrafluoroborate (pages 2019–2025)

      Recep Ucan, Umit Tunca and Gurkan Hizal

      Article first published online: 15 MAY 2003 | DOI: 10.1002/pola.10753

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      The controlled polymerization of methyl methacrylate (MMA) in bulk was initiated with p-chlorobenzenediazonium tetrafluoroborate (1) and Cu(II) or Cu(I)/Cu(II)/N,N,N′,N″,N″-pentamethyldietylene triamine (PMDETA) complex system at various temperatures (room temperature, 60, and 90 °C). The proposed polymerization mechanism is based on the Meerwein-type arylation reaction followed by a reverse atom transfer radical polymerization. In this mechanism, aryl radicals formed by the reaction with 1 and PMDETA initiated the polymerization of MMA in the presence of Cu(II)/PMDETA complex.

    5. Synthesis of autophotosensitive hyperbranched polyimides based on 3,3′,4,4′-benzophenonetetracarboxylic dianhydride and 1,3,5-tris(4-aminophenoxy)benzene via end capping of the terminal anhydride groups by ortho-alkyl aniline (pages 2026–2035)

      Huan Chen and Jie Yin

      Article first published online: 19 MAY 2003 | DOI: 10.1002/pola.10747

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      A series of soluble and autophotosensitive hyperbranched polyimides first were synthesized by an in situ end-capping reaction of the terminal anhydride groups of benzophenone-containing, anhydride-terminated hyperbranched poly(amic acid)s with ortho-alkyl aniline and then were chemically imidized. Thermogravimetric analysis revealed their excellent thermal stability. The patterning evaluation results indicated that the autophotosensitive polymers had a good photolithographic property with a resolution greater than 3 μm.

    6. Pore size modification of macroporous crosslinked poly(dicyclopentadiene) (pages 2036–2046)

      Alberto Della Martina, László Garamszegi and Jöns G. Hilborn

      Article first published online: 19 MAY 2003 | DOI: 10.1002/pola.10749

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      This article describes the pore size modification and in situ surface functionalization of macroporous crosslinked poly(dicyclopentadiene) (PDCPD), produced by chemically induced phase separation, with newly synthesized norbornene end-functionalized poly(ethylene glycol) (PEG) oligomers. The incorporation of these telechelic oligomers allowed a substantial decrease in the pore size and a related increase in the internal surface area. The resulting porous materials were characterized by scanning electron microscopy, density measurements, nitrogen adsorption, and mercury porosimetry.

    7. Metal-template synthesis of cyclic epoxide–amine oligomers: Uncrosslinked epoxide–amine addition polymers, 47 (pages 2047–2052)

      Joachim E. Klee, Klaus Hägele and Michael Przybylski

      Article first published online: 20 MAY 2003 | DOI: 10.1002/pola.10752

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      The addition reaction of 2,2-bis-[4-(2,3-epoxypropoxy)-phenyl]-propane (DGEBA) and preformed complexes of metal ions and disecondary diamines led to a large quantity of cyclic epoxide–amine oligomers. In the fast atom bombardment mass spectra the molecular ions of the n = 1-cycle of DGEBA and N,N′-dibenzyl-5-oxanonanediamine-1,9 are detected at m/z = 681.

    8. Synthesis of poly(chitosan-N-isopropylacrylamide) complex particles with the method of soapless dispersion polymerization (pages 2053–2063)

      Chia-Fen Lee, Chia-Jen Wen and Wen-Yen Chiu

      Article first published online: 20 MAY 2003 | DOI: 10.1002/pola.10733

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      Crosslinked poly(chitosan-N-isopropylacrylamide) [poly(NIPAAM-chitosan)] complex particles were successfully synthesized with the method of soapless dispersion polymerization. The anionic initiator ammonium persulfate (APS) and the cationic initiator 2,2′-azobis(2-methylpropionamidine) dihydrochloride (AIBA) were used to initiate the copolymerization. The poly(NIPAAM-chitosan) copolymer particles synthesized with APS as the initiator had a homogeneous morphology, whereas the copolymer particles synthesized with AIBA as the initiator showed a core–shell morphology. In addition, various variables such as the particle size, reaction rate, and ζ potential were taken into account.

    9. Dark-cure studies of cationic photopolymerizations of epoxides: Characterization of the active center lifetime and kinetic rate constants (pages 2064–2072)

      Vishal Sipani and Alec B. Scranton

      Article first published online: 20 MAY 2003 | DOI: 10.1002/pola.10750

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      We have characterized the effective rate constants for termination/trapping (kt/t) and propagation (kp) for solvent-free cationic photopolymerizations of phenyl glycidyl ether for conversions up to 50%. We have performed dark-cure experiments in which active centers are produced photochemically for a specified period of time until the initiating light is shuttered off, and then the polymerization rate is monitored in the dark. This method is especially well suited for characterizing cationic polymerizations because of the long active center lifetimes. Our analysis provides profiles of the instantaneous kinetic rate constants as functions of conversion (or time). For photopolymerizations of phenyl glycidyl ether initiated with iodonium photoinitiators, kt/t and kp remain essentially invariant for conversions up to 50%.

    10. Synthesis and characterization of multiblock copolymers based on L-lactic acid, citric acid, and poly(ethylene glycol) (pages 2073–2081)

      Fanglian Yao, Yun Bai, Yutao Zhou, Chang Liu, Hao Wang and Kangde Yao

      Article first published online: 20 MAY 2003 | DOI: 10.1002/pola.10756

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      To improve the hydrophilicity of poly(L-lactic acid) (PLLA) and accelerate its degradation rate as well as introduce the functionalized pendant groups to PLLA, citric acid was selected as the comonomer. Also, multiblock copolymers poly(L-lactic-co-citric acid) (PLCA)-PLLA and PLCA-poly(ethylene glycol) were synthesized and characterized.

    11. Cocrystallization phenomena in piperazine-based copolyamides as examined by differential scanning calorimetry, wide-angle X-ray diffraction, and solid-state NMR (pages 2082–2094)

      Bert Vanhaecht, Jan Devroede, Rudolph Willem, Monique Biesemans, Wyjayanthi Goonewardena, Sanjay Rastogi, Sven Hoffmann, Philip G. Klein and Cor E. Koning

      Article first published online: 21 MAY 2003 | DOI: 10.1002/pola.10751

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      Copolyamides 2.14/piperazine.14 with variable built-in ratios of 1,2-ethylenediamine (1,2-EDA) and piperazine (pip) were synthesized by solution polycondensation. The gradual substitution of 1,2-EDA units with cycloaliphatic pip units in polyamide 2.14 resulted in a progressively decreased melting (Tm) and crystallization temperature of the obtained copolyamides. Apparently, the Tm raising effect of the incorporation of rigid cycloaliphatic moieties is overruled by the simultaneous Tm reduction caused by a decreasing hydrogen-bond density. Indications for cocrystallization of the 2.14 and pip.14 repeating units were obtained by thermal and wide-angle X-ray diffraction analysis of both the copolyamides 2.14/pip.14 and a blend of both homopolyamides. Supportive indications were collected from solid-state NMR analysis of the respective homo- and copolyamides.

    12. Vinyl-type polymerization of norbornene by nickel(II) bisbenzimidazole catalysts (pages 2095–2106)

      Abhimanyu O. Patil, Stephen Zushma, Robert T. Stibrany, Steven P. Rucker and Louise M. Wheeler

      Article first published online: 21 MAY 2003 | DOI: 10.1002/pola.10725

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      Novel nickel(II) bisbenzimidazole complexes were prepared via a three-step synthetic procedure consisting of aniline/diacid condensation, ligand N-alkylation, and metal complexation. The complexes were characterized by X-ray crystallography and found to possess a pseudotetrahedral geometry. Upon activation with methylaluminoxane, these nickel bisbenzimidazoles did not polymerize simple olefins (e.g., ethylene, propylene, and 1-butene) but were found to carry out the rapid and efficient polymerization of norbornene. 13C NMR suggested that the polymerization occurred via vinyl addition (i.e., a 2,3-linked polymer); no ring-opened product was observed. Thermogravimetric analysis indicated that the polynorbornenes were stable up to 400 °C under nitrogen.

    13. Ring-opening metathesis polymerization as a route to controlled copolymers of ethylene and polar monomers: Synthesis of ethylene–vinyl chloride-like copolymers (pages 2107–2116)

      Hongli Yang, Manirul Islam, Charles Budde and Stuart J. Rowan

      Article first published online: 21 MAY 2003 | DOI: 10.1002/pola.10759

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      Linear ethylene–vinyl chloride-like copolymers were successfully synthesized via bulk ring-opening metathesis polymerization of 5-chlorocyclooctene and 5,6-dichlorocyclooctene, followed by diimide reduction. In addition, a series of polymers with different chlorine contents were also prepared by the copolymerization of 5-chlorocyclooctene with cyclooctene.

    14. Highly active methyl methacrylate polymerization catalysts obtained from bis(3,5-dinitro-salicylaldiminate)nickel(II) complexes and methylaluminoxane (pages 2117–2124)

      Carlo Carlini, Marco Martinelli, Anna Maria Raspolli Galletti and Glauco Sbrana

      Article first published online: 21 MAY 2003 | DOI: 10.1002/pola.10758

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      The homopolymerization of methyl methacrylate was studied in the presence of catalysts based on bis(3,5-dinitro-salicylaldiminate)nickel(II) complexes and methylaluminoxane. The influence of the reaction parameters and the structure of the nickel precursors on the polymer characteristics and catalyst activity was investigated. The activation of the catalytic systems by an ethylene atmosphere during their preparation was also studied.

    15. Kinetics of the ring-opening metathesis polymerization of a 7-oxanorbornene derivative by Grubbs' catalyst (pages 2125–2131)

      Marium G. Holland, Veronica E. Griffith, Marcia B. France and Steven G. Desjardins

      Article first published online: 21 MAY 2003 | DOI: 10.1002/pola.10761

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      The kinetics of the initiation and propagation of the ring-opening metathesis polymerization of exo,exo-5,6-bis(methoxycarbonyl)-7-oxabicyclo[2.2.1]hept-2-ene (4) catalyzed by Grubbs' catalyst [Cl2(PCy3)2Ru[DOUBLE BOND]CHPh, or 2] were measured by ultraviolet–visible and 1H NMR spectroscopy, respectively. Activation parameters for these processes were also determined. Although the ratio of the rate constant of initiation to the rate constant of propagation was determined to be less than 1 for this system, this polymerization showed many of the characteristics of a living system, including low polydispersities.

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