Journal of Polymer Science Part A: Polymer Chemistry

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

15 November 2001

Volume 39, Issue 22

Pages 3851–4049

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communication
    4. Articles
    1. Synthesis and characterization of new hyperbranched poly(aryl ether oxadiazole)s (pages 3851–3860)

      Fang-Iy Wu and Ching-Fong Shu

      Version of Record online: 28 SEP 2001 | DOI: 10.1002/pola.10028

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      A new AB2 monomer containing two phenolic hydroxyl groups and an oxadiazole ring-activated aryl fluoride was synthesized for use in the preparation of a hyperbranched poly(aryl ether oxadiazole) with phenolic terminated groups. Aromatic nucleophilic substitution of the aryl fluoride with the phenolates resulted in ether linkages and, subsequently, the hyperbranched poly(aryl ether oxadiazole) having approximately a 44% degree of branching. The terminal phenolic groups were readily functionalized. The nature of the chain-end groups significantly influences physical properties such as the glass-transition temperature and solubility of the modified polymers.

    2. From well-defined diblock copolymers prepared by a versatile atom transfer radical polymerization method to supramolecular assemblies (pages 3861–3874)

      Maxime Ranger, Marie-Christine Jones, Marie-Andrée Yessine and Jean-Christophe Leroux

      Version of Record online: 2 OCT 2001 | DOI: 10.1002/pola.10029

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      The synthesis of well-defined diblock copolymers by atom transfer radical polymerization was explored in detail for the development of new poly(ethylene glycol) (PEG)-based colloidal carriers. The copolymerization of hydrophobic and ionizable monomers, using the PEG macroinitiator, made it possible to modulate the physicochemical properties of the resulting polymers in solution. Depending on the length and nature of the hydrophobic segment, the nonionic copolymers could self-assemble in water into nanoparticles or polymeric micelles. The amphiphilic and nonionic copolymers could be suitable for the solubilization and delivery of water-insoluble drugs, whereas the ionic diblock copolymers offer promising characteristics for the delivery of electrostatically charged compounds through the formation of polyion complex micelles.

    3. Physicochemical and thermal studies of viscose rayon borate fiber and its carbon fiber (pages 3875–3883)

      Young Gun Ko, Ung Su Choi, Dong June Ahn, Jeong Su Kim and Tae Young Kim

      Version of Record online: 2 OCT 2001 | DOI: 10.1002/pola.10047

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      Borate was synthesized onto viscose rayon felt by a surface reaction. Coupling and carbonization were confirmed by attenuated total reflectance Fourier transform infrared (ATR FTIR). The coupling and initial carbonization temperatures were certified with ATR FTIR, elemental analysis of carbon, and thermogravimetric analysis. The activation energy of borate-coupled viscose rayon decreased much more than before coupling. However, the activation energy increased with the increasing carbonization temperature in the carbonization step. In this article, the relationship between the activation energy and limiting oxygen index value is studied.

    4. Copolycondensations of bisphenols with aggregates of isophthalic acid and terephthalic acid activated by tosyl chloride/dimethylformamide/pyridine in different manners (pages 3884–3892)

      Fukuji Higashi, Takayo Shirai, Kiyoshi Mitani and Kanako Sugishita

      Version of Record online: 28 SEP 2001 | DOI: 10.1002/pola.10045

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      A mixture of isophthalic acid (IPA) and terephthalic acid (TPA) was activated by tosyl chloride (TsCl)/dimethylformamide (DMF)/pyridine (Py) in two steps via the treatment of a mixture of the initially activated IPA/TPA with additional TPA or IPA followed by the activation of TPA. The resulting mixture was different in several ways from a mixture obtained by the activation of them all at once. An evaluation was made that was based on the solubility in Py, the melting points, the IR spectra of a mixture of dimethyl esters of IPA and TPA produced by quenching with methanol, and the thermal properties and NMR spectra of thermotropic copolyesters from methylhydroquinone and chlorohydroquinone.

    5. Synthesis and polymerization of new styryl and methacryloyl monomers containing acidic saccharide moieties (pages 3893–3901)

      Yoshiaki Shimura, Kazuhiko Hashimoto, Chiaki Yamanaka and Daisuke Setojima

      Version of Record online: 28 SEP 2001 | DOI: 10.1002/pola.10046

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      New styryl-type water-insoluble and methacryloyl-type water-soluble monomers, N-(p-vinylbenzyl)-1,2-O-isopropylidene-6-D-glucofuranuronamide (3) and N-(2-methacryloylamino)ethyl-1,2-O-isopropylidene-6-D-glucofuranuronamide (4), were synthesized from the most common acidic saccharide, D-glucuronic acid (1). Their homopolymers and copolymers, with many reactive reducing moieties in the pendants, were obtained through radical homopolymerizations and copolymerizations with styrene and acrylamide followed by the deprotection of the resulting polymers. Their pendant reducing ends may be useful as potential binding sites under a hydrophilic atmosphere.

    6. Pulsed-laser polymerization-gel permeation chromatographic determination of the propagation-rate coefficient for the methyl acrylate dimer: A sterically hindered monomer (pages 3902–3915)

      Kenta Tanaka, Bunichiro Yamada, Christopher M. Fellows, Robert G. Gilbert, Thomas P. Davis, Lachlan H. Yee, Gregory B. Smith, Mark T. L. Rees and Gregory T. Russell

      Version of Record online: 2 OCT 2001 | DOI: 10.1002/pola.10034

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      The methyl acrylate dimer (MAD) is a sterically hindered macromonomer, and the propagating radical can fragment to an unsaturated end group. The propagation-rate coefficient (kp) for MAD obtained by pulsed-laser polymerization is given by kp/dm3 mol−1 s−1 = 106.1 exp(−29.5 kJ mol−1). The Arrhenius parameters are consistent with an increased activation energy and reduced frequency factor as compared with acrylate or methacrylate; both of these changes can be ascribed to hindrance.

    7. Biodegradation of copolymers composed of optically active L-lactide and (R)- or (S)-1-methyltrimethylene carbonate (pages 3916–3927)

      Chikara Tsutsumi and Hajime Yasuda

      Version of Record online: 2 OCT 2001 | DOI: 10.1002/pola.10035

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      Enhanced biodegradability was observed with the introduction of optically active (R)- or (S)-1-methyltrimethylene carbonate or rac-1-methyltrimethylene carbonate into poly(L-lactide) sequences in 58/42 to 94/6 ratios. The result was the formation of poly(L-lactide-co-1-methyltrimethylene carbonate), which showed high enzymatic degradability with proteinase K.

    8. Application of novel polymers with S-alkylsulfonium salt moieties as alkylating agents and thermal latent cationic initiators (pages 3928–3933)

      Osamu Shimomura, Ikuyoshi Tomita and Takeshi Endo

      Version of Record online: 4 OCT 2001 | DOI: 10.1002/pola.10036

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      Sulfonium-containing polymers with dibenzothiophenium and diphenylsulfonium moieties were applied as both alkylating agents and latent initiators for the cationic polymerization of glycidyl phenyl ether (5). The alkylation of acetonitrile proceeded smoothly with poly(S-n-octyl-2-vinyldibenzothiophenium tetrafluoroborate) (4) to give N-(n-octyl)acetamide (2) in an excellent yield. The cationic polymerization of 5 was also carried out in the presence of poly(sulfonium salt)s (6 or 10), with which a moderate thermal latent activity of the polymeric catalysts was confirmed.

    9. Controlled polymerization of acrylic acid under 60Co irradiation in the presence of dibenzyl trithiocarbonate (pages 3934–3939)

      Chun-Yan Hong, Ye-Zi You, Ru-Ke Bai, Cai-Yuan Pan and Gereltu Borjihan

      Version of Record online: 4 OCT 2001 | DOI: 10.1002/pola.10042

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      The polymerization of acrylic acid (AA) performed under 60Co irradiation in the presence of dibenzyl trithiocarbonate at room temperature displays living polymerization, and a well-defined poly(acrylic acid) with a low polydispersity index was successfully prepared directly from AA for the first time. This polymerization undergoes homolytic cleavage of weak bond—monomer addition—reversible termination of a chain radical with a stable radical process.

    10. Particle formation under monomer-starved conditions in the semibatch emulsion polymerization of styrene. I. Experimental (pages 3940–3952)

      S. Sajjadi

      Version of Record online: 3 OCT 2001 | DOI: 10.1002/pola.10031

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      Particle formation in a semibatch emulsion polymerization of styrene under monomer-starved conditions was studied. The semibatch emulsion polymerization reactions were started by the monomer being fed at a low rate to a reaction vessel containing deionized water, an emulsifier, and an initiator. The number of particles increased with a decreasing monomer feed rate. The results showed a higher dependence of the number of particles on the emulsifier and initiator concentrations compared with that for a batch emulsion polymerization. The formation of a large number of polymer particles reduced the average radical number of particles to a very low value (≪0.50). The particle size distribution of the latexes broadened with time as a result of stochastic broadening.

    11. Side-chain functionalized liquid-crystalline polymers and blends. IX. Phase behavior and structure of comb-shaped liquid-crystalline ionomers containing calcium ions (pages 3953–3959)

      E. B. Barmatov, D. A. Pebalk, M. V. Barmatova and V. P. Shibaev

      Version of Record online: 3 OCT 2001 | DOI: 10.1002/pola.10043

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      Liquid-crystalline ionomers with oxycyanobiphenyl mesogenic groups containing 2–15 mol % calcium ions were synthesized. The incorporation of metal ions in the polymer leads to some rise in the clearing point and glass-transition temperature accompanied by the induction of the smectic A phase. Calcium ions act both as points of noncovalent electrostatic binding (ionic crosslinks) of polymer chains and are capable of forming larger ionic associates (multiplets). The formation of ionic links leads to the structure defects suppressing growth of the mesophase clearing temperature.

    12. Atom transfer radical copolymerization of N-phenylmaleimide and styrene initiated with dendritic polyarylether 2-bromoisobutyrate (pages 3960–3966)

      You-Liang Zhao, Jing Jiang, Hong-Wei Liu, Chuan-Fu Chen and Fu Xi

      Version of Record online: 4 OCT 2001 | DOI: 10.1002/pola.10040

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      Dendritic polyarylether 2-bromoisobutyrates with different generations (Gn-Br, n = 1–3) as macroinitiators for the controlled free-radical polymerization of N-phenylmaleimide (PhMI) and styrene were investigated. The copolymerization carried out in anisole with CuBr/bpy catalyst afforded polymers with well-defined molecular weights and low polydispersities (1.12 < Mw/Mn < 1.35). When the molar fraction of PhMI was 0.50, the apparent activation enthalpy of copolymerization was 38.2 kJ/mol. Effects of monomer feed on the apparent activation enthalpy and copolymer composition were also studied. According to the Kelen–Tüdős method, the monomer reactivity ratios were determined to be rPhMI = 0.0325 and rSt = 0.0524, respectively.

    13. Substituent effect on the cationic ring-opening polymerization of acyloxymethyl five-member cyclic dithiocarbonates (pages 3967–3980)

      Alexander Steblyanko, Wonmun Choi, Fumio Sanda and Takeshi Endo

      Version of Record online: 4 OCT 2001 | DOI: 10.1002/pola.10037

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      Five-member cyclic dithiocarbonates were synthesized by the reactions of carbon disulfide with benzoic, p-anisic, p-chlorobenzoic, 1-naphthalenecarboxylic, p-nitrobenzoic, and p-(tert-butyl)benzoic glycidyl esters, and their cationic ring-opening polymerizations were carried out with methyl trifluoromethane sulfonate and trifluoromethane sulfonic acid as initiators at room temperature to 80 °C. The data of the reaction kinetics, NMR studies, and molecular orbital calculations proved a plausible mechanism involving the participation of p-substituted benzoxymethyl groups to stabilize the cationic propagating end.

    14. Photophysical characteristics of soluble oligo(p-phenylenevinylene)–fullerene dyad (pages 3981–3988)

      Junlin Yang, Hongzhen Lin, Shu Wang, Yuliang Li, Fenglian Bai and Daoben Zhu

      Version of Record online: 4 OCT 2001 | DOI: 10.1002/pola.10051

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      An alternating conjugated oligomer of alkylated carbazole and dialkoxyl-substituted phenylene, with pendant C60 moieties, (PPV-AFCAR) was prepared and characterized. The excited-state properties of PPV–AFCAR were investigated with steady-state spectroscopy and lifetime measurements. After photoexcitation, photoinduced energy transfer from the oligomer chain to the pendant moiety occurred in great proportion, but a charge-separation process did not. Whether the energy-transfer process was measurable or not depended on the system temperature. At 77 K, a quantum yield of more than 50% for energy transfer was found by the fitting of a linear combination of the excitation spectra of the precursor oligomer, the alternating conjugated oligomer of alkylated carbazole and dialkoxyl-substituted phenylene PPV–ACAR, and the absorption spectra of C60.

    15. Preparation and characterization of soluble terpolymers from m-phenylenediamine, o-anisidine, and 2,3-xylidine (pages 3989–4000)

      Xin-Gui Li, Wei Duan, Mei-Rong Huang and Yu-Liang Yang

      Version of Record online: 4 OCT 2001 | DOI: 10.1002/pola.10041

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      A series of terpolymers were synthesized by oxidative polymerization of m-phenylenediamine, o-anisidine, and 2,3-xylidine in HCl and characterized by IR, ultraviolet–visible, 1H NMR, and solid-state 13C NMR spectroscopies; X-ray diffraction; and thermogravimetry. The terpolymers are soluble in organic solvents and indeed contain three monomer units. The actual composition determined by 13C NMR is close to the feed composition, although the o-anisidine content calculated by the 1H NMR spectrum of the soluble part of the terpolymer is higher than the feed o-anisidine content. The terpolymers and m-phenylenediamine homopolymer exhibit a higher polymerization yield, much higher intrinsic viscosity, and more amorphism than poly(o-anisidine). The terpolymers show an increased thermostability and degradation activation energy with an increasing o-anisidine content.

    16. In situ atom transfer radical polymerization of styrene with a tetraethylthiuram disulfide/copper bromide/2,2′-bipyridine initiating system (pages 4001–4008)

      Peng Li and Kun-Yuan Qiu

      Version of Record online: 4 OCT 2001 | DOI: 10.1002/pola.10050

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      In situ atom transfer radical polymerization (ATRP) of styrene has been successfully carried out with TD/CuBr2/bpy. The initiator dtc—Br and catalyst CuBr were both produced from TD and CuBr2 in the reaction system. The polymerization process had some characteristics of living radical polymerization. The Mn increased linearly with the monomer conversion corresponding to 0.5-initiator efficiency, and Mw/Mn was rather low, 1.30. PSt-b-PMMA could be obtained with the resulting PSt[BOND]Br catalyzed by CuBr/bpy or CuCl/bpy through a conventional ATRP pathway. Comparison experiments demonstrated the radical nature of the polymerization.

  2. Rapid Communication

    1. Top of page
    2. Articles
    3. Rapid Communication
    4. Articles
    1. Formation rate constants of the mayo dimer in the autopolymerization of styrene (pages 4009–4013)

      Thomas Kothe and Hanns Fischer

      Version of Record online: 4 OCT 2001 | DOI: 10.1002/pola.10052

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      Absolute rate constants and their Arrhenius parameters are obtained for the bimolecular formation of the Mayo dimer during the induction time of the spontaneous polymerization of styrene from the zero-order decay of the stable nitroxide 2,2,6,6-tetramethylpiperidine-1-oxyl, which is followed by electron spin resonance.

  3. Articles

    1. Top of page
    2. Articles
    3. Rapid Communication
    4. Articles
    1. Synthesis and properties of novel cardo aromatic poly(ether-benzoxazole)s (pages 4014–4021)

      Sheng-Huei Hsiao and Ming-Hsiang He

      Version of Record online: 5 OCT 2001 | DOI: 10.1002/pola.10039

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      A series of poly(o-hydroxy amide)s having both ether and cardo groups were synthesized via the low-temperature solution polycondensation of 1,1-bis[4-(4-chloroformylphenoxy)phenyl]cyclohexane (1a), 5,5-bis[4-(4-chloroformylphenoxy)phenyl]-4,7-methanohexahydroindan (1b), and 9,9-bis[4-(4-chloroformylphenoxy)phenyl]fluorene (1c) with three bis(o-aminophenol)s including 4,4′-diamino-3,3′-dihydroxybiphenyl (2), 3,3′-diamino-4,4′-dihydroxybiphenyl (3), and 2,2-bis(3-diamino-4-hydroxyphenyl)hexafluoropropane (4). Subsequent thermal cyclodehydration of the poly(o-hydroxy amide)s afforded poly(ether-benzoxazole)s. Basic characterization of the poly(o-hydroxy amide) prepolymers and polybenzoxazoles is described.

    2. 2,2,6,6-Tetramethyl-1-piperidinyl-oxyl/[bis(acetoxy)-iodo]benzene-mediated oxidation: A versatile and convenient route to poly(ethylene glycol) aldehyde or carboxylic acid derivatives (pages 4022–4024)

      Christophe Masson, Daniel Scherman and Michel Bessodes

      Version of Record online: 5 OCT 2001 | DOI: 10.1002/pola.10049

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      The oxidation of different poly(ethylene glycol) derivatives via a 2,2,6,6-tetramethyl-1-piperidinyl-oxyl/[bis(acetoxy)-iodo]benzene system led to the corresponding aldehyde and carboxylic acid derivatives in high yields with easy processing.

    3. Synthesis and characterization of novel crosslinkable polymers with a nonlinear optical chromophore as a pendant group (pages 4025–4034)

      Sung-Ho Jin, Sung-Hyun Kim and Yeong-Soon Gal

      Version of Record online: 5 OCT 2001 | DOI: 10.1002/pola.10044

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      New crosslinkable polymers with a nonlinear optical active chromophore as a side group were synthesized by condensation chain polymerization via palladium-catalyzed carbon–carbon coupling reactions. The absorption of the ultraviolet–visible spectrum of the resulting polymers was drastically reduced after thermal curing at 160 °C. The electrooptic coefficient (r33) measured at 1.3 μm ranged from 7 to 15 pm/V.

    4. Liquid-crystalline organic–inorganic hybrid polymers with functionalized silsesquioxanes (pages 4035–4043)

      Kyung-Min Kim and Yoshiki Chujo

      Version of Record online: 5 OCT 2001 | DOI: 10.1002/pola.10048

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      New liquid-crystalline (LC) hybrid polymers containing silsesquioxanes with different contents of mesogens were synthesized from polyhedral oligomeric silsesquioxane (POSS) macromonomer and LC monomer by radical copolymerization. Their liquid crystallinities and thermal stabilities were very dependent on the POSS segments of hybrid polymers behaving as hard, compact components. Also, the unusual monotropic LC behavior of Cube-LC90, the hybrid polymer with 90 mol % LC moiety, was attributed to the hindrance of POSS moieties for the reorientation of randomized LC molecules during the cooling cycle. Cube-LC90 showed a smectic-phase-like fine-grained texture and better stability with respect to the LC homopolymer. The obtained LC hybrid polymers were soluble in common solvents such as tetrahydrofuran, toluene, and chloroform.

    5. Amine–quinone polyimides (pages 4044–4049)

      Mijeong Han and David E. Nikles

      Version of Record online: 5 OCT 2001 | DOI: 10.1002/pola.10027

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      Two dianiline monomers were prepared by the reaction of either 4,4′-methylenedianiline or 4,4′-oxydianiline with 1,4-benzoquinone. These monomers were used to synthesize a series of amine–quinone polyimides by condensation with either 3,3′,4,4′-benzophenonetetracarboxylic dianhydride or 4,4′-(hexafluoroisopropylidene) diphthalic anhydride to make the corresponding polyamic acid. The polyamic acids were converted to the polyimides by thermal imidization at 290 °C. The amine–quinone polyimides gave freestanding films with tensile strengths in the range of 90 to 150 Mpa and Young's moduli of 0.9 to 1.5 Gpa. The thermal decomposition temperature under nitrogen was 440 to 480 °C and the glass-transition temperature was in the range of 280 to 310 °C. The amine–quinone polyimides had the excellent thermal and mechanical properties that one expects for polyimides.