Journal of Polymer Science Part A: Polymer Chemistry

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

15 December 2002

Volume 40, Issue 24

Pages 4387–4580

  1. Articles

    1. Top of page
    2. Articles
    3. Note
    4. Articles
    1. Synthesis and characterization of block copolymers from 2-vinylnaphthalene by anionic polymerization (pages 4387–4397)

      Faquan Zeng, Mu Yang, Jianxin Zhang and Sunil K. Varshney

      Article first published online: 28 OCT 2002 | DOI: 10.1002/pola.10524

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      The AB-type block copolymers of 2-vinylnaphthalene with methyl methacrylate, tert-butyl acrylate, and hexamethylcyclotrisiloxane were synthesized by living anionic polymerization in tetrahydrofuran or toluene. The molecular weight was characterized by a laser scattering method, and the results were compared with those from size exclusion chromatography. The effects of the purification method, the solvents for anionic polymerization, and the mechanism of block copolymerization were examined in detail.

    2. Preparation of a copolymer of methyl methacrylate with a new monomer, 2,2,6,6-tetramethyl-4-benzyloxyl-piperidinyl methacrylate, and its initiation of the graft copolymerization of styrene with a controlled radical mechanism (pages 4398–4403)

      Haitao Zhang, Zhenrong Guo and Junlian Huang

      Article first published online: 28 OCT 2002 | DOI: 10.1002/pola.10525

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      A copolymer [P(MMA-co-TBPM)] was prepared by the radical polymerization of methyl methacrylate (MMA) and 2,2,6,6-tetramethyl-4-benzyloxyl-piperidinyl methacrylate (TBPM) with azobisisobutyronitrile as an initiator. TBPM was a new monomer containing an activated ester. Both the copolymer and TBPM were characterized with NMR, IR, and gel permeation chromatography in detail. It was confirmed that P(MMA-co-TBPM) could initiate the graft polymerization of styrene by the cleavage of the activated ester of the TBPM segment. This process was controllable, and the molecular weight of the graft chain of polystyrene increased with the increment of conversion.

    3. Synthesis of a novel block copolymer poly(ethylene oxide)-block-poly(4-vinylpyridine) by combination of anionic ring-opening and controllable free-radical polymerization (pages 4404–4409)

      Guangqiang Lu, Zhongfan Jia, Wen Yi and Junlian Huang

      Article first published online: 28 OCT 2002 | DOI: 10.1002/pola.10526

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      The block copolymer poly(ethylene oxide)-b-poly(4-vinylpyridine) was synthesized by a combination of living anionic ring-opening polymerization and a controllable radical mechanism. The poly(ethylene oxide) prepolymer with the 2,2,6,6-tetramethylpiperidinyl-1-oxy end group (PEOT) was first obtained by anionic ring-opening polymerization of ethylene oxide with sodium 4-oxy-2,2,6,6-tetramethylpiperidinyl-1-oxy as the initiator in a homogeneous process. UV and electron spin resonance spectroscopy determined that in the polymerization the 2,2,6,6-tetramethylpiperidinyl-1-oxy moiety was left intact. The copolymers were then obtained by radical polymerization of 4-vinylpyridine in the presence of PEOT. The polymerization showed a controllable radical mechanism. The desired block copolymers were characterized by gel permeation chromatography, Fourier transform infrared, and NMR spectroscopy in detail.

    4. Kinetic study of the nitroxide-mediated controlled free-radical polymerization of n-butyl acrylate in aqueous miniemulsions (pages 4410–4420)

      Céline Farcet, Julien Nicolas and Bernadette Charleux

      Article first published online: 29 OCT 2002 | DOI: 10.1002/pola.10531

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      The controlled free-radical homopolymerization of n-butyl acrylate was studied in aqueous miniemulsions with a low molar mass alkoxyamine unimolecular initiator and an acyclic β-phosphonylated nitroxide mediator, N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) nitroxide, also called SG1. The system led to stable latex particles composed of well-defined poly(n-butyl acrylate).

    5. Substituent effects on the chain-transfer behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane in the presence of disulfides and thiols (pages 4421–4425)

      Simon Harrisson, Thomas P. Davis, Richard A. Evans and Ezio Rizzardo

      Article first published online: 29 OCT 2002 | DOI: 10.1002/pola.10528

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      The chain-transfer behavior of 7-methylene-2-methyl-1,5-dithiacyclooctane was investigated in the presence of four chain-transfer agents: thiophenol (PhSH), thiobenzoic acid (BzSH), diphenyl disulfide (PhSSPh), and dibenzoyl disulfide (BzSSBz). The chain-transfer constants for these compounds at 60 °C were 0.38 (PhSH), 0.76 (BzSH), 0.24 (PhSSPh), and 0.05 (BzSSBz). The variations in the thiol chain-transfer constants could be explained in terms of the stability of the resulting radicals. The chain transfer to the disulfides, however, appeared to be determined by the electronic character of the disulfide bond, and this suggests that the transfer took place via an addition–fragmentation mechanism.

    6. Ethylene/1-octene copolymerization studies with in situ supported metallocene catalysts: Effect of polymerization parameters on the catalyst activity and polymer microstructure (pages 4426–4451)

      Colin Li Pi Shan, João B. P. Soares and Alexander Penlidis

      Article first published online: 29 OCT 2002 | DOI: 10.1002/pola.10533

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      Ethylene and 1-octene copolymerizations were carried out with an in situ supported Me2Si(2-Me-4,5 BenzInd)2ZrCl2. In this investigation, a factorial experimental design was carried out to examine the effect of polymerization temperature and ethylene pressure, presence of hydrogen and alkylaluminum activator, and level of comonomer in the feed, on the catalyst activity, short chain branching distribution, and molecular weight distribution of the polymer. Temperature had the most remarkable effect on the polymer microstructure. At high 1-octene levels, the short chain branching distribution of the copolymer broadened significantly with decreasing temperature.

    7. Synthesis and characterization of novel luminescent polymers with alternate phenothiazine and divinylbenzene units (pages 4452–4462)

      Tzi-Yi Wu and Yun Chen

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10530

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      Novel luminescent polymers (P1 and P2) carrying alternate phenothiazine and divinylbenzene units were synthesized via the Wittig reaction. Compared with reported hole-transport groups such as carbazole, alkyldiphenylamine, triphenylamine, and iminodibenzyl chromophores, phenothiazine moieties in P1 and P2 bathochromically shift the PL maxima and narrow the band gaps. The highest occupied molecular orbitals of P1 (4.78 eV) and P2 (4.74 eV) were even higher than the work function of ITO electrode (4.8 eV). The threshold electric fields of the Al/P1 (or P2)/ITO device were smaller than P3, consisting of alternate iminodibenzyl and divinylbenzene units.

    8. SEC-MALDI-TOF mass spectral characterization of a hyperbranched polyether prepared via melt transetherification (pages 4463–4476)

      M. Jayakannan, Joost L. J. Van Dongen, Girish Ch. Behera and S. Ramakrishnan

      Article first published online: 4 NOV 2002 | DOI: 10.1002/pola.10527

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      An AB2 monomer, 1-(2-hydroxyethoxy)-3,5-bis-(methoxymethyl)-2,4,6-trimethylbenzene, was synthesized from mesitol and melt-polycondensed in the presence of an acid catalyst via a transetherification process at 145–150 °C to yield a soluble, moderately high molecular weight hyperbranched polyether (weight-average molecular weight = 64,600, weight-average molecular weight/number-average molecular weight = 5.2). The origin of the broad molecular weight distribution, which could either be intrinsic to such hyperbranched structures or be due to structural heterogeneity, was further probed by the fractionation of the samples by size exclusion chromatography and by the subjection of each fraction to matrix-assisted laser desorption/ionization time-of-flight mass spectral analysis. The mass spectral analysis suggested the presence of two primary types of species: one corresponding to the simple branched structure and the other to macrocyclics. Interestingly, from the relative intensities of the two peaks, it was apparent that cyclization became favorable at higher conversions in the melt transetherification process.

    9. Micellar polymerization of amphiphilic poly(vinyl alcohol) macromonomer having a methacrylate end group prepared by aldol-type group-transfer polymerization (pages 4477–4484)

      Akinori Takasu, Shigeki Ohmori, Yutaka Yamauchi and Tadamichi Hirabayashi

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10538

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      Amphiphilic and heterotactic-rich poly(vinyl alcohol) (PVA) macromonomer, that is, PVA having a phenyl or phenoxyethyl methacrylate unit as the polymerizable end group, was synthesized via the aldol-type group-transfer polymerization (Aldol-GTP) technique. Aldol-GTPs of vinyloxytriethylsilane (VOTES) proceeded smoothly to give silylated PVA macromonomers (number-average molecular weight: 1.3 × 103–1.96 × 104). Poly(VOTES) was easily desilylated to give heterotactic-rich PVA macromonomer in good yield. The critical micelle concentration of the PVA macromonomer was determined by surface-tension measurement. Micellar polymerization of the amphiphilic macromonomer as the first attempt for PVA macromonomer gave comb-shaped polymer having PVA side chains effectively (conversion: 80–82%).

    10. New fluorinated thermoplastic elastomers. I. The synthesis and thermal characteristics of α,ω-dihydrosilane hybrid fluorinated polysiloxane precursors (pages 4485–4492)

      S. Andre, F. Guida-Pietrasanta, A. Rousseau, B. Boutevin and G. Caporiccio

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10534

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      The synthesis of new α,ω-dihydrosilane hybrid fluorinated polysiloxanes is described via the polycondensation between a diallyl perfluorinated compound and tetramethyldisiloxane. The diallyl perfluorinated compound is prepared from a perfluorinated α,ω-diido compound and allyl acetate, and this is followed by zinc deiodoacetalization. The length of the polysiloxane chains influences the glass-transition temperature and thermal stability of the fluorinated oligomers.

  2. Note

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    2. Articles
    3. Note
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      Synthesis and characterization of soluble main-chain hydrazone polymers (pages 4493–4497)

      Min Ju Jeong, Beom Jin Kim and Ji Young Chang

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10537

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      Bisacetoacetamides having two 1,3-diketo groups were prepared by the reaction of aromatic amines with diketene. The polymers were prepared by the diazo coupling reaction of bisacetoacetamides with aromatic diazonium salts under mild basic conditions. They had hydrazone structures, stabilized by intramolecular hydrogen bonding, in the solid and solution states. The polymer having sulfonyl groups was very sensitive to pH change in a dimethyl sulfoxide solution and existed in hydrazone-azo anion equilibrium under basic conditions.

  3. Articles

    1. Top of page
    2. Articles
    3. Note
    4. Articles
    1. Star polymer synthesis using trithiocarbonate functional β-cyclodextrin cores (reversible addition–fragmentation chain-transfer polymerization) (pages 4498–4512)

      Martina H. Stenzel and Thomas P. Davis

      Article first published online: 1 NOV 2002 | DOI: 10.1002/pola.10532

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      The preparation of seven-arm polystyrene star polymers grown from β-cyclodextrin cores via the reversible addition–fragmentation chain-transfer process is reported. Polymerizations have been performed at three different temperatures in the presence of various amounts of trithiocarbonate groups. A remarkable deviation of the obtained molecular weight from the expected weight has been observed and is discussed. Furthermore, the synthesis of stars with block structures in each arm is presented.

    2. 13C NMR and electron spin resonance analyses of the radical polymerization of diisopropyl itaconate (pages 4513–4522)

      Tomohiro Hirano, Kazuhiro Furuya, Makiko Seno and Tsuneyuki Sato

      Article first published online: 5 NOV 2002 | DOI: 10.1002/pola.10529

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      Electron spin resonance (ESR) spectra of polymerizations of diisopropyl itaconate were found to consist of two kinds of resonances due to radicals with different conformations. The relative intensity ratios of the resonances varied with the intramolecular chain-transfer reaction. The syndiotacticities of the obtained polymers also decreased with the intramolecular chain-transfer reaction. These results suggested that the propagating radicals with different stereosequences near the chain end had different ESR spectral patterns, probably because of the difference in conformation.

    3. Biodegradable network elastomeric polyesters from multifunctional aromatic carboxylic acids and poly(ϵ-caprolactone) diols (pages 4523–4529)

      Minoru Nagata, Masao Kanechika, Wataru Sakai and Naoto Tsutsumi

      Article first published online: 1 NOV 2002 | DOI: 10.1002/pola.10539

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      Novel biodegradable network polyesters were prepared from multifunctional aromatic carboxylic acids [trimesic acid (Y), pyromellic acid (X), and mellic acid (YM)] and poly(ϵ-caprolactone) (PCL) diols with molecular weights of 530, 1250, and 2000. Some network polyester films, including YPCL1250, XPCL1250, and YMPCL2000, showed elastomeric properties with high ultimate elongation and low tensile modulus. The rate of enzymatic degradation increased with the increasing molecular weight of the PCL diols, but it decreased in the order of YPCL > XPCL > YMPCL.

    4. Alternating copolymerization of propylene oxide with carbon monoxide catalyzed by Co complex and Co/Ru complexes (pages 4530–4537)

      Daisuke Takeuchi, Yoshihiko Sakaguchi and Kohtaro Osakada

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10542

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      A Co-based catalyst promotes the ring-opening alternating copolymerization of propylene oxide with carbon monoxide and yields a polyester. The head-to-tail linkage of the polymer is highly regulated.

    5. Telomerization of vinylidene fluoride with alkyl (or aryl) trifluoromethanethiosulfonates (pages 4538–4549)

      Bruno Ameduri, Thierry Billard and Bernard Langlois

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10535

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      The photochemical-induced telomerization of vinylidene fluoride (VDF) with cyclohexyl (or phenyl) trifluoromethanethiosulfonate (CF3SO2SR), leading to CF3(VDF)nSR telomers, where R stands for cyclohexyl or phenyl, is presented.

    6. Synthesis and characterization of novel biodegradable poly(ester amide) with ether linkage in the backbone chain (pages 4550–4555)

      Ming Xia Li, Ren Xi Zhuo and Fan Qi Qu

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10547

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      New biodegradable poly(ester amide)s were synthesized via ring-opening copolymerization of a hydrophilic monomer 3-morpholinone (M) with ε-caprolactone (CL) with stannous octoate, aluminum isopropoxide or aluminium isobutoxide as the intiator. The comonomer reactivity ratios were determined (M 0.74 and CL 1.28). Introducing various M contents into the copolymer P(M-co-CL) backbone resulted in improved hydrophilicity and led to a faster degradation rate. Controlled release of 5-Fluorouracil with the copolymers is investigated.

    7. Attempt to investigate the temperature effect on polycondensation from the solution copolyesterification of preformed oligomers and bisphenols with tosyl chloride/dimethylformamide/pyridine (pages 4556–4562)

      Fukuji Higashi, Ryohsuke Hayashi and Harumi Ohno

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10540

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      In an attempt to investigate the temperature effect on polycondensation, a two-stage copolycondensation of an equimolar mixture of isophthalic acid (IPA) and terephthalic acid (TPA) first with a bisphenol and then with another bisphenol was studied at 80 and 120 °C. The results were examined with respect to the change in the way in which the preformed oligomers reacted with the subsequent monomers by an analysis of the sequences of the subsequent monomers in the resultant copolymers by NMR.

    8. Facile synthesis of hyperbranched polyimides from A2 + BB2 monomers (pages 4563–4569)

      Ye Liu and Tai-Shung Chung

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10545

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      Hyperbranched polyimides were prepared by the polymerization of A2 + BB2 monomers, performed by mixing the monomers together in N-methylpyrrolidone (NMP) at 17% w/v concentrations with the molar ratio of A2/BB2 ranging from 1:1 to 2:1. No gelation happened during the polymerization processes, probably because of the lower reactivity of 2-amino than of 4-/6-amino in BB2 as demonstrated by 1H NMR. 1H NMR analysis showed that the degrees of branching of the polymers increased from 36 to 83% with increasing molar ratios of A2/BB2 from 1:1 to 2:1.

    9. Synthesis and optical and electrochemical properties of novel copolymers containing alternating 2,3-divinylquinoxaline and hole-transporting units (pages 4570–4580)

      Tzi-Yi Wu and Yun Chen

      Article first published online: 12 NOV 2002 | DOI: 10.1002/pola.10541

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      For the enhancement of charge affinity, electron-affinitive 2,3-divinylquinoxaline and a series of hole-transporting chromophores (iminodibenzyl, phenothiazine, dihexyloxybenzene, and didodecyloxydistyrylbenzene) were incorporated alternately into the polymeric main chain. The resulting copolymers (P1P4) were basically amorphous materials and were thermally stable below 300 °C. The electronic structures, photoluminescence, and electrochemical properties of these copolymers were mainly determined by the electron-donating chromophores in the backbone. They showed significant positive solvatochromism in formic acid. An electrochemical study revealed that they exhibited lower band gaps (<2.3 eV) due to alternating donor and acceptor conjugated units (push–pull structure). Single-layer light-emitting diodes of aluminum, P1P4, and indium tin oxide glass were fabricated, and preliminary electroluminescence spectra showed that P1, P3, and P4 were orange-emitting materials.

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