Journal of Polymer Science Part A: Polymer Chemistry

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

1 October 2001

Volume 39, Issue 19

Pages 3199–3473

  1. Articles

    1. Top of page
    2. Articles
    3. Articles
    4. Articles
    1. Microemulsion polymerization of styrene stabilized by sodium dodecyl sulfate and short-chain alcohols (pages 3199–3210)

      Chorng-Shyan Chern and Long-Jiang Wu

      Version of Record online: 7 AUG 2001 | DOI: 10.1002/pola.1302

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      Styrene microemulsion polymerizations with different short-chain alcohols as the cosurfactant were investigated. The desorption of radicals out of latex particles played an important role in the reaction kinetics. The maximal polymerization rate in decreasing order was C6OH > C4OH > C5OH; this was related to the differences in the water solubility of CiOH (i = 4, 5, or 6) and the structure of the oil–water interface. A water-insoluble dye was used in a study of the particle nucleation mechanisms.

    2. Synthesis and properties of poly(arylene ether)s bearing sulfonic acid groups on pendant phenyl rings (pages 3211–3217)

      Kenji Miyatake and Allan S. Hay

      Version of Record online: 8 AUG 2001 | DOI: 10.1002/pola.1303

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      Two kinds of new poly(arylene ether)s containing sulfonic acid groups were synthesized. Polymer 1 composed of tetraphenylphenylene ether and perfluorobiphenylene units was sulfonated with chlorosulfonic acid. Sulfonation took place only at the para position of the pendant phenyl rings. The average degree of sulfonation per repeating unit (m) was controlled from 1–4. Sulfonated polymer 2 with m = 3 was soluble in methanol and dimethyl sulfoxide and swelled in water. Incorporating bis(3,5-dimethylphenyl)sulfone moieties into the sulfonated polymer imparts less methanol affinity. Polymers 4 with 30–65 mol % tetrakis(sulfophenyl)phenylene ether units had high decomposition temperatures above 300 °C, hydrophilicity, and good hydrolytic stability.

    3. Synthesis and proton conductivities of phosphonic acid containing poly-(arylene ether)s (pages 3218–3226)

      Y. Z. Meng, S. C. Tjong, A. S. Hay and S. J. Wang

      Version of Record online: 7 AUG 2001 | DOI: 10.1002/pola.1304

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      A phosphonic acid containing bisphenol was successfully synthesized from phenolphthalein and m-aminophenylphosphonic acid. A series of homo- and copoly-(arylene ether)s containing phosphonic acid groups were prepared by solution nucleophilic polycondensation. These poly-(arylene ether)s had very high glass-transition temperatures ranging from 254 to >315 °C and high conductivities ranging from 10−5 to 10−6 Scm−1 analyzed by the Cole–Cole method. The phosphonic acid containing poly-(arylene ether)s provide an alternative for preparing proton-exchange polymer membranes.

    4. Polar, functionalized diene-based materials. V. Free-radical polymerization of 2-[(N-benzyl-n-methylamino)methyl]-1,3-butadiene and copolymerization with styrene (pages 3227–3238)

      Lifen Wu and Valerie V. Sheares

      Version of Record online: 7 AUG 2001 | DOI: 10.1002/pola.1305

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      2-[N-Benzyl-N-methylamino)methyl]-1,3-butadiene (BMAMBD), the first asymmetric tertiary amino-containing diene-based monomer, was synthesized and polymerized by bulk and solution free-radical polymerization. Typical kinetics were observed, giving polymers with 〈Mn〉 values of approximately 20 × 103 to 50 × 103 g/mol (where Mn is the number-average molecular weight) and polydispersity indices near 1.5. To further tailor polymer properties, we synthesized copolymers with styrene. The composition of the random copolymers ranged from 17 to 93% of the amino diene monomer with glass-transition temperatures of 64–7 °C, respectively.

    5. Analysis of ethylene oxide sequences of the acetal copolymer from trioxane and ethylene oxide (pages 3239–3245)

      Naoaki Yamasaki, Kenji Kanaori and Junzo Masamoto

      Version of Record online: 10 AUG 2001 | DOI: 10.1002/pola.1306

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      By a linear combination of the 1H NMR spectrum of each oxyethylene unit of the three polymeric model compounds, we have succeeded in determining the ethylene oxide sequence by the 1H NMR method for the copolymer from trioxane and ethylene oxide. Good agreement was observed between the 1H NMR method and the hydrolysis method for the analysis of the ethylene oxide sequences.

    6. Self-initiating performance of maleic anhydride on surface photografting polymerization (pages 3246–3249)

      Jian-Ping Deng and Wan-Tai Yang

      Version of Record online: 8 AUG 2001 | DOI: 10.1002/pola.1307

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      Maleic anhydride (MAH) was readily photografted onto low-density polyethylene (LDPE) film by UV irradiation in the solid and liquid states without photoinitiators and further initiated the photografting polymerization of acrylic acid as a photoinitiator. The self-initiating performance was attributed to the ability of MAH to abstract hydrogen atoms from LDPE film when irradiated with UV radiation.

    7. Poly(ethylene terephthalate) copolyesters derived from (2S,3S)-2,3-dimethoxy-1,4-butanediol (pages 3250–3262)

      Darwin P. R. Kint, Emilia Wigström, Antxon Martínez de Ilarduya, Abdelilah Alla and Sebastián Muñoz-Guerra

      Version of Record online: 9 AUG 2001 | DOI: 10.1002/pola.1308

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      Random poly(ethylene terephthalate) (PET) copolyesters containing (2S,3S)-2,3-dimethoxy-1,4-butanediol were prepared by a two-step melt polycondensation with molecular weights between 16,000 and 44,000. They showed higher water affinity than PET and displayed optical activity. Melting and glass-transition temperatures decreased with copolymerization. Crystalline copolymers with butanediol contents up to 30 mol % adopt the same crystalline structure as PET.

    8. Synthesis and characterization of fully aromatic thermotropic liquid-crystalline copolyesters containing m-hydroxybenzoic acid units (pages 3263–3277)

      Zekeri̇ya Yerli̇kaya, Serpi̇l Aksoy and Erdal Bayramli

      Version of Record online: 10 AUG 2001 | DOI: 10.1002/pola.1309

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      Fully aromatic copolyesters containing linear units over 67 mol % exhibited nematic liquid-crystalline phases in a broad temperature range. The melting of the flow temperatures was found to be in the processable region. Thermal transitions, optical properties, sequence distribution, and randomness of the monomer units in the polymer chains, intrinsic viscosity, and degree of crystallinity of the copolyesters depend on the type of linear monomer unit. Intrinsic viscosity and degree of crystallinity decreased as a result of the incorporation of kink monomer units in the polymer.

    9. Synthesis and characterization of alternating copolymers containing triphenylamine as hole-transporting units (pages 3278–3286)

      Hongchao Li, Yanhou Geng, Shuwen Tong, Hui Tong, Rong Hua, Guangping Su, Lixiang Wang, Xiabin Jing and Fosong Wang

      Version of Record online: 9 AUG 2001 | DOI: 10.1002/pola.1310

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      A series of poly(p-phenylene vinylene)s containing triphenylamine units were synthesized via Wittig reactions in good yields. The trans-vinylene double bonds were confirmed by Fourier transform infrared and NMR spectroscopy. The polymers possessed high molecular weights and exhibited good thermal stability. They were soluble in common organic solvents and exhibited intense photoluminescence. The electrochemical measurements suggested that the polymers possessed a good hole-transporting property due to the incorporation of triphenylamine moieties.

    10. End-capped AB3-type hyperbranched carbosilane macromolecules (pages 3287–3293)

      Chungkyun Kim and Hyojeong Kim

      Version of Record online: 13 AUG 2001 | DOI: 10.1002/pola.1311

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      End-capped carbosilane macromolecules were prepared via the hydrosilation and continual addition of phenylethynyl, amine, bis(trimethylsilyl)amine, and cholesterol groups on the AB3-type hyperbranched carbosilane polymer. The matrix-assisted laser desorption/ionization time-of-flight mass spectroscopic views of the end-capped hyperbranched carbosilanes agreed with the expected mass distribution, in close regularity.

    11. Copolymerization of propylene with various higher α-olefins using silica-supported rac-Me2Si(Ind)2ZrCl2 (pages 3294–3303)

      Jun-Ting Xu, Yin-Bang Zhu, Zhi-Qiang Fan and Lin-Xian Feng

      Version of Record online: 13 AUG 2001 | DOI: 10.1002/pola.1312

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      The copolymerization of propylene with 1-hexene, 1-octene, 1-decene, and 1-dodecene was carried out with silica-supported rac-Me2Si(Ind)2ZrCl2 as a catalyst. The activities and polymer structures of the homogeneous and supported catalysts were compared. The supported catalyst incorporated more comonomer than the homogeneous catalyst at the same monomer feed ratio. Supporting the metallocene also improved the stereoregularity and regioregularity of the copolymers. Low mobility of the propagation chain in the supported catalyst was suggested as the reason for the different polymerization behaviors of the supported catalyst with the homogeneous system.

    12. Copolymerization behavior of direct polycondensation of AB2 and AB monomers that forms hyperbranched aromatic polyamide copolymers (pages 3304–3310)

      Mitsutoshi Jikei, Ken Fujii and Masa-Aki Kakimoto

      Version of Record online: 13 AUG 2001 | DOI: 10.1002/pola.1313

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      The direct copolymerization of 3,5-bis-(4-aminophenoxy)benzoic acid (AB2 monomer) and 3-(4-aminophenoxy)benzoic acid (AB monomer) (50/50) was carried out in the presence of condensation agents. Spectroscopic data for growing molecules revealed that the AB2 monomer was incorporated faster than the AB monomer, and dendritic units formed slowly, mainly at the late stage of the copolymerization. The stepwise copolymerization of the AB2 and AB monomers gave copolymers that had different architectures. The solubility of the stepwise copolymers was low, and the inherent viscosity was high in comparison with the one-step random copolymer.

    13. Kinetics of thiol–ene and thiol–acrylate photopolymerizations with real-time fourier transform infrared (pages 3311–3319)

      Neil B. Cramer and Christopher N. Bowman

      Version of Record online: 13 AUG 2001 | DOI: 10.1002/pola.1314

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      We used real-time Fourier transform infrared to monitor the conversion of both thiol and ene (vinyl) functional groups independently during photoinduced thiol–ene and thiol–acrylate photopolymerizations. With kinetic expressions for thiol–acrylate polymerizations, the acrylate propagation kinetic constant was found to be 1.5 times greater than the rate constant for hydrogen abstraction from the thiol. Conversions of thiol–acrylate systems of various initial stoichiometries were successfully predicted with this ratio of propagation and chain-transfer kinetic constants. Thiol–ene network properties and photopolymerizations with and without the use of a photoinitiator were explored.

    1. Microemulsion polymerization of acrylamide and styrene: Effect of the structures of reaction media (pages 3320–3334)

      Jingcheng Hao

      Version of Record online: 15 AUG 2001 | DOI: 10.1002/pola.1315

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      We determined the microemulsion structures of two systems, cetyltrimethylammonium bromide (CTAB)/n-butanol/10% n-octane/water and sodium dodecyl sulfonate (As)/n-butanol/20% styrene/water, by conductivity measurements to investigate the polymerization of acrylamide and styrene in the microemulsion systems. The polymerization kinetics of acrylamide in CTAB micelles and microemulsion media were studied. The maximum polymerization rate in CTAB micelles was found at the second critical micelle concentration. A connection between the structures of the microemulsions and the polymerization rates of acrylamide was observed, and the polyacrylamide molecular weights, which depended on the structures of the microemulsions, were also found. A similar connection between the structures of the microemulsions and the conversions of styrene in As/n-butanol/20% styrene/water was observed again. The structures of the microemulsions had an important role in the molecular weights and sizes of polystyrene.

  2. Articles

    1. Top of page
    2. Articles
    3. Articles
    4. Articles
    1. Synthesis and characterization of novel polyimide from bis-(3-aminophenyl)-4-(trifluoromethyl)phenyl phosphine oxide (pages 3335–3347)

      Kwang Un Jeong, Young-Jun Jo and Tae-Ho Yoon

      Version of Record online: 13 AUG 2001 | DOI: 10.1002/pola.1316

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      A novel diamine, bis-(3-aminophenyl)-4-(trifluoromethyl)phenyl phosphine oxide (mDA3FPPO), containing phosphine oxide and fluorine moieties was prepared via the Grignard reaction from an intermediate, 4-(trifluoromethyl)phenyl diphenyl phosphine oxide (3FPPO), that was synthesized from diphenylphosphinic chloride and 4-(trifluoromethyl)bromobenzene, followed by nitration and reduction. The monomer was used to prepare polyimides with a number of dianhydrides such as pyromellitic dianhydride (PMDA), 5,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethyliden]-bis-1,3-isobenzofuranedione (6FDA), 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, or 4,4′-oxydiphthalic dianhydride (ODPA). The polyimides prepared with mDA3FPPO provided high glass-transition temperatures (248–311 °C), good thermal stability, excellent solubility, low birefringence (0.0030–0.0036), low dielectric constants (2.9–3.1), and excellent adhesive properties with Cu foil (107 g/mm).

    1. Durable and refreshable polymeric N-halamine biocides containing 3-(4′-vinylbenzyl)-5,5-dimethylhydantoin (pages 3348–3355)

      Yuyu Sun and Gang Sun

      Version of Record online: 15 AUG 2001 | DOI: 10.1002/pola.1317

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      A novel functional vinyl-hydantoin monomer, 3-(4′-vinylbenzyl)-5,5-dimethylhydantoin, was made into its homopolymer and copolymers with vinyl acetate, acrylonitrile, and methyl methacrylate. The polymers were characterized with Fourier transform infrared and 1H NMR, and their thermal properties were analyzed with differential scanning calorimetry studies. The halogenated products of the corresponding copolymers exhibited potent antibacterial properties against Escherichia coli, and the antibacterial properties were durable and regenerable. The structure–property relationships of the polymers were further discussed.

    2. Ultrasonically initiated emulsion polymerization of methyl methacrylate (pages 3356–3364)

      Yongqin Liao, Qi Wang, Hesheng Xia, Xi Xu, Steven M. Baxter, Robert V. Slone, Shuguang Wu, Graham Swift and David G. Westmoreland

      Version of Record online: 15 AUG 2001 | DOI: 10.1002/pola.1318

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      The ultrasonically initiated emulsion polymerization of methyl methacrylate (MMA) was investigated. The surfactant sodium dodecyl sulfonate (SDS) plays a very important role in obtaining a high polymer yield and serves as an initiator and interfacial modifier; the monomer conversion increases with increasing SDS concentration. An increasing reactor temperature and an increasing N2 purging rate leads to an increase in the MMA conversion. The MMA conversion decreases with increasing MMA concentration. Under optimized reaction conditions, a high MMA conversion of about 67% and a high molecular weight of several millions can be obtained in about 30 min.

  3. Articles

    1. Top of page
    2. Articles
    3. Articles
    4. Articles
    1. Synthesis of phosphate-pendant polymers and their application to thermally latent polymeric initiators (pages 3365–3370)

      Moon Suk Kim, Fumio Sanda and Takeshi Endo

      Version of Record online: 15 AUG 2001 | DOI: 10.1002/pola.1319

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      A novel phosphate monomer, O-p-(methacryloyloxymethyl)benzyl O,O-diethyl phosphate (MDP) was synthesized by the reaction of diethyl phosphorochloridate with 1,4-benzenedimethanol, followed by the reaction with methacryloyl chloride in the presence of triethylamine. The radical polymerization of MDP and copolymerization with methyl methacrylate were carried out in the presence of 2,2′-azobisisobutyronitrile (3 mol %) in dimethylacetamide at 60 °C for 20 h to afford phosphate-pendant polymers. The polymerization of glycidyl phenyl ether (GPE) was carried out with the phosphate-pendant polymer as an initiator in the presence of ZnCl2. The polymerization did not proceed below 90 °C but rapidly proceeded above 90 °C to afford polyGPE. The phosphate-pendant polymer served as a good thermally latent polymeric initiator.

    2. New polymer syntheses. CIX. Biodegradable, alternating copolyesters of terephthalic acid, aliphatic dicarboxylic acids, and alkane diols (pages 3371–3382)

      Abbas-Ali Shaik, Martin Richter, Hans R. Kricheldorf and Ralph-P. Krüger

      Version of Record online: 17 AUG 2001 | DOI: 10.1002/pola.1320

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      Biodegradable polyesters with an alternating sequence of terephthalic acid, aliphatic dicarboxylic acids, and aliphatic diols were prepared with three different methods and characterized with respect to their chemical structures and thermal properties.

    3. Hyperbranched polymers from propargyloxysilanes: New types of acetylenic resins (pages 3383–3391)

      Yingxin Xiao and David Y. Son

      Version of Record online: 16 AUG 2001 | DOI: 10.1002/pola.1321

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      Propargyloxysilanes are polymerized to hyperbranched polymers in good yields using platinum catalysis. The terminal ethynyl groups undergo crosslinking reactions and can be chemically modified.

    4. From metal-catalyzed radical telomerization to metal-catalyzed radical polymerization of vinyl chloride: Toward living radical polymerization of vinyl chloride (pages 3392–3418)

      A. D. Asandei and V. Percec

      Version of Record online: 16 AUG 2001 | DOI: 10.1002/pola.1322

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      The metal-catalyzed radical polymerization of vinyl chloride (VC) in ortho-dichlorobenzene initiated with various activated halides and metal catalysts is reported. Poly(vinyl chloride) with molecular weights larger then the theoretical limit allowed by chain transfer to VC were obtained even at 130 °C. The most elemental features of a living radical polymerization were observed for systems based on iodine-containing initiators and Cu(0), that is, I[BOND]CH2[BOND]Ph[BOND]CH2[BOND]I/Cu(0)/bpy (where bpy = 2,2′-bipyridyl), at 130 °C. However, because of the formation of inactive species via chain transfer to VC and other side reactions, the conversions were lower than 40%. A mechanistic interpretation of the chain transfer to monomer in the presence of Cu species is proposed.

    5. High-refractive-index thin films prepared from aminoalkoxysilane-capped pyromellitic dianhydride–titania hybrid materials (pages 3419–3427)

      Chao-Ching Chang and Wen-Chang Chen

      Version of Record online: 17 AUG 2001 | DOI: 10.1002/pola.1323

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      High-refractive-index aminoalkoxysilane-capped pyromellitic dianhydride–titania hybrid optical thin films were synthesized and characterized in this study. Through adjustments in the concentration and reaction time, the inorganic content in the films could be as high as 59.1 wt %. The prepared films had a nanosized domain of the TiO2 segment. An atomic force microscopy study suggested that they had excellent film planarity. The refractive indices of the films at 633 nm increased linearly from 1.567 to 1.780 with increasing titania content. However, the Abbe numbers of the films showed an opposite trend. Excellent optical transparence was obtained in the visible region for the films.

    6. Synthesis and luminescence of polyphosphazenes with carbazolyl side chains (pages 3428–3433)

      Zhen Li, Jingui Qin, Xianyu Deng and Yong Cao

      Version of Record online: 17 AUG 2001 | DOI: 10.1002/pola.1324

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      Two new blue-light-emitting polyphosphazenes containing carbazolyl groups as side chains were synthesized. An electroluminescent diode was fabricated, and a bright blue light was observed; the maximum external quantum efficiency was about 0.026% at an applied forward voltage of 23 V.

    7. Anomalous solubility of polyacrylamide prepared by dispersion (precipitation) polymerization in aqueous tert-butyl alcohol (pages 3434–3442)

      Suparna Guha, Biswajit Ray and Broja M. Mandal

      Version of Record online: 17 AUG 2001 | DOI: 10.1002/pola.1325

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      The dispersion (precipitation) polymerization of acrylamide in aqueous t-butyl alcohol (TBA) media yields polymers that are only partially soluble when the TBA concentrations are in the range 82 vol % < TBA < 95 vol %. The anomalous solubility has been attributed to polymer-transfer reactions occurring during the solid-phase polymerization followed by crosslinking. Above 95% TBA, the polymer swells so little that its glass-transition temperature remains above the polymerization temperature, and no solid-phase reaction is possible. Below 82% TBA, the polymer swells so much that the polymer-transfer reaction becomes unimportant compared with transfer to monomer and solvent. The replacement of TBA by acetone or methanol removes the solubility anomaly because of the high chain-transfer ability of these solvents compared with that of TBA.

    8. Synthesis of poly(methyl methacrylate) in a pyridine solution by atom transfer radical polymerization (pages 3443–3450)

      José Luis de la Fuente, Marta Fernández-García, Marina Fernández-Sanz and Enrique López Madruga

      Version of Record online: 17 AUG 2001 | DOI: 10.1002/pola.1326

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      Pyridine was used as a solvent for the atom transfer radical polymerization (ATRP) of methyl methacrylate. The homopolymerizations were carried out with methyl 2-halopropionate (MeXPr, where X was Cl or Br) as an initiator, copper halide (CuX) as a catalyst, and 2,2′-bipyridine as a ligand from 80 to 120 °C. The mixed halogen system methyl 2-bromopropionate/copper chloride was also used. For all the initiator systems used, the polymerization reaction showed linear first-order rate plots, a linear increase in the number-average molecular weight with conversion, and relatively low polydispersities. In addition, the dependence of the polymerization rate on the temperature is presented. These data are compared with those obtained in bulk, demonstrating the effectiveness of this solvent for this monomer in ATRP.

    9. New concept of positive photosensitive polyimide: Reaction development patterning (RDP) (pages 3451–3463)

      Takafumi Fukushima, Toshiyuki Oyama, Takao Iijima, Masao Tomoi and Hiroshi Itatani

      Version of Record online: 17 AUG 2001 | DOI: 10.1002/pola.1327

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      A soluble polyimide without any pendant alkaline reactive groups showed good positive photosensitivity in the presence of diazonaphthoquinone (DNQ) by UV irradiation, followed by development with ethanolamine-containing solution. The resulting polyimide pattern exhibited 10-μm L/S resolution with ∼20-μm film thickness.

    10. Reverse atom transfer radical polymerization of vinyl monomers with Fe[SC(S)NEt2]3 alone as the catalyst (pages 3464–3473)

      Dong-Qi Qin, Shu-Hui Qin and Kun-Yuan Qiu

      Version of Record online: 17 AUG 2001 | DOI: 10.1002/pola.1328

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      The living radical polymerization of vinyl monomers was successfully carried out with diethyl 2,3-dicyano-2,3-diphenylsuccinate/ferric tri(diethyldithiocarbamate) as a novel ligand-free reverse atom transfer radical polymerization initiation system. Poly(methyl methacrylate) and polystyrene with high molecular weights and quite narrow polydispersities were obtained. 1H NMR spectroscopy revealed the presence of an α-(carbethoxycyanophenyl)methyl group and an ω-diethyldithiocarbamate (DC) group. Various chain-extension reactions and block copolymerizations were successfully conducted under UV light and thermal treatments, respectively, to prove the presence and efficient reinitiating of the ω-DC group.