Journal of Polymer Science Part A: Polymer Chemistry

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

15 February 2002

Volume 40, Issue 4

Pages 429–631

  1. Articles

    1. Top of page
    2. Articles
    1. Polyimides based on 2,5-bis(4-aminophenoxy)biphenyl (pages 429–438)

      Chin-Ping Yang and Ruei-Shin Chen

      Version of Record online: 2 JAN 2002 | DOI: 10.1002/pola.10116

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      A series of aromatic, organosoluble polyimides and copolypyromellitimides bearing pendent phenyl groups were synthesized from 2,5-bis(4-aminophenoxy)biphenyl with six kinds of commercial dianhydrides via a conventional two-stage process. These polymers were characterized by high solubility in N-methyl-2-pyrrolidone and m-cresol, good film-forming ability, a wide temperature range between the glass-transition temperature and decomposition temperature, and outstanding thermal stability together with excellent tensile properties. Excellent properties of these polyimides are attributed to the incorporation of pendent phenyl groups in the diamine.

    2. Amphiphilic diblock, triblock, and star block copolymers by living radical polymerization: Synthesis and aggregation behavior (pages 439–450)

      Amilcar Pillay Narrainen, Sagrario Pascual and David M. Haddleton

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10122

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      Copper(I)-mediated living radical polymerization was used to synthesize amphiphilic block copolymers of poly(n-butyl methacrylate) and poly[(2-dimethylamino)ethyl methacrylate]. Functionalized bromo poly(n-butyl methacrylate) macroinitiators were prepared from monofunctional, difunctional, and trifunctional initiators: 2-bromo-2-methylpropionic acid 4-methoxyphenyl ester, 1,4-(2′-bromo-2′-methyl-propionate)benzene, and 1,3,5-(2′-bromo-2′-methylpropionato)benzene.

    3. Synthesis and characterization of monomers and polymers for adhesives from methyl oleate (pages 451–458)

      Shana P. Bunker and Richard P. Wool

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10130

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      A new monomer was synthesized from a fatty acid methyl ester that was capable of forming high molecular weight polymers. The starting material, methyl oleate, was functionalized using acrylic acid. The polymer was formed via emulsion polymerization. A monomer conversion of approximately 91% was achieved, and a maximum weight-average molecular weight of approximately 106 g/mol was observed.

    4. Synthesis and properties of aromatic poly(ester amide)s with pendant phosphorus groups (pages 459–470)

      Guey-Sheng Liou and Sheng-Huei Hsiao

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10129

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      Two series of phosphorus-containing aromatic poly(ester amide)s with good solubility and thermal stability were prepared by low-temperature solution polycondensation from 1,4-bis(3-aminoben- zoyloxy)-2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)naphthalene (m-3) and 1,4-bis(4-aminobenzoyloxy)-2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)naphthalene (p-3) with various aromatic diacid chlorides. Transparent, tough, and flexible films of these polymers were cast from N,N-dimethylacetamide and N-methyl-2-pyrrolidone solutions. Their casting films had tensile strengths of 71–214 MPa, elongations to break of 5–10%, and initial moduli of 2.3–6.0 GPa.

    5. Ethylene copolymerization with cyclic dienes using rac-Et[Ind]2ZrCl2–Methylaluminoxane (pages 471–485)

      Adriane G. Simanke, Raquel S. Mauler and Griselda B. Galland

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10133

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      The effect of the copolymerization temperature and amount of comonomer in the copolymerization of ethylene with 1,3-cyclopentadiene, dicyclopentadiene, and 4-vinyl-1-cyclohexene and the rac-Et[Ind]2ZrCl2–methylaluminoxane metallocene system was studied. Dicyclopentadiene was the most reactive comonomer among the cyclic dienes studied. 1,3-Cyclopentadiene dimerized into dicyclopentadiene during the copolymerization, giving a terpolymer of ethylene–dicyclopentadiene–cyclopentadiene.

    6. Solid polymer electrolytes III: Preparation, characterization, and ionic conductivity of new gelled polymer electrolytes based on segmented, perfluoropolyether-modified polyurethane (pages 486–495)

      Chi-Chang Chen, Wuu-Jyh Liang and Ping-Lin Kuo

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10119

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      New segmented polyurethanes with perfluoropolyether (PFPE) and poly(ethylene oxide) blocks were synthesized from PFPE diol, poly(ethylene glycol) (PEG), 2,4-toluene diisocyanate, and ethylene glycol. Fourier transform infrared, NMR, and thermal analysis (differential scanning calorimetry and thermogravimetric analysis) were used to characterize the structures of these copolymers. These copolymers exhibited phase segregation; the glass-transition temperature of PEG increased with an increased content of the PFPE segment, and the glass-transition temperature of the soft segment of the copolymer decreased remarkably with propylene carbonate as a solvent. The ionic conductivity of these gelled copolymer electrolytes was influenced by the composition, the content of the liquid electrolyte, and the temperature. The ionic conductivities of these systems were about 10−3 S cm−1 at room temperature and 10−2 S cm−1 at 70 °C.

    7. Synthesis and characterization of soluble, fluorescent poly(arylene ether)s, poly(arylene thioether)s, and poly(arylene sulfone)s containing 1,3,5-triphenylbenzene segments (pages 496–510)

      Abbas-Alli G. Shaikh and Allan S. Hay

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10136

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      A phenyl-substituted m-terphenyl diol was converted into high molecular weight poly(arylene ether)s. A bisphenol was also converted via N,N-dimethyl-O-thiocarbamate into a masked dithiol that was polymerized directly with activated difluoro compounds in the presence of a mixture of Cs2CO3 and CaCO3 as a base in diphenyl sulfone as a solvent. The resulting poly(arylene sulfide)s were oxidized into polysulfones that were then selectively sulfonated on the pendant phenyl group.

    8. Sulfobetaine zwitterionomers based on n-butyl acrylate and 2-ethoxyethyl acrylate: Monomer synthesis and copolymerization behavior (pages 511–523)

      Mario Gauthier, Tony Carrozzella and Alexander Penlidis

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10138

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      Zwitterionic methacrylate monomers (15) were synthesized in high yields and copolymerized with n-butyl acrylate and 2-ethoxyethyl acrylate. Copolymerization reactivity ratios were estimated for the 10 corresponding binary acrylate–methacrylate systems with statistically sound analysis techniques and were correlated with the sulfobetaine monomer structure.

    9. Organosoluble and light-colored fluorinated polyimides from 4,4′-bis(4-amino-2-trifluoromethylphenoxy)biphenyl and aromatic dianhydrides (pages 524–534)

      Chin-Ping Yang, Sheng-Huei Hsiao and Mao-Feng Hsu

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10113

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      A series of novel fluorinated polyimides were prepared from 4,4′-bis(4-amino-2-trifluoromethylphenoxy)biphenyl 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.

    10. Preparation and emission properties of various poly(dimethylsilylenearylenevinylene)s: Effects of geometric structures and π units on their emission properties (pages 535–543)

      Giseop Kwak and Toshio Masuda

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10139

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      trans-Poly(dimethylsilylenearylenevinylene)s (trans-rich) and cis-poly(dimethylsilylenearylenevinylene)s (cis-rich) containing phenylene, biphenylene, and phenylenesilylenephenylene units were prepared by hydrosilylation catalyzed with the RhI(PPh3)3 complex. UV spectra of the trans-type polymers showed redshifts and hyperchromic effects with respect to those of the cis-type ones, and the quantum yields of emission of the former polymers were much higher than those of the latter polymers. The quantum yield of the trans-rich polymer with the biphenylene moiety was as large as 0.15. The effects of the geometric structure and π unit on the absorption and emission properties of these polymers were examined with molecular orbital methods.

    11. Microstructure analysis and thermal property of copolymers made of glycolide and ϵ-caprolactone by stannous octoate (pages 544–554)

      Ji Won Pack, Soo Hyun Kim, I-Whan Cho, Soo Young Park and Young Ha Kim

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10123

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      The reactivity ratios of the glycolyl unit (rG) and caproyl unit (rC) were calculated from monomer sequences and measured as 6.84 and 0.13, respectively. Mechanistic considerations based on reactivity ratios, monomer consumption data, and average sequence lengths are discussed. The unusual phase diagram of glycolide/ϵ-caprolactone copolymers implies that the copolymer melting temperature does not depend on its composition alone but rather on the nature of the sequence distribution.

    12. (Thiocarbonyl-α-thio)carboxylic acid derivatives as transfer agents in reversible addition–fragmentation chain-transfer polymerizations (pages 555–563)

      Steven C. Farmer and Timothy E. Patten

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10143

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      Ethyl S-(thiobenzoyl)thioacetate, ethyl S-thiobenzoyl-2-thiopropionate, and S-(thiobenzoyl)thioglycolic acid were used as chain-transfer agents for the reversible–addition fragmentation chain-transfer polymerizations of styrene, methyl methacrylate (MMA), and butyl acrylate (BA). Of these polymerizations, only those of styrene and BA with any of the transfer agents showed molecular weight control corresponding to controlled/living polymerizations. Semiempirical PM3 calculations indicated that the molecular weight control of the polymerizations correlated with the stability trend of the leaving-group radical of the chain-transfer agent.

    13. Reactivity ratios for the terpolymerization of methyl methacrylate, vinyl acetate, and molecular oxygen (pages 564–572)

      Priyadarsi De and D. N. Sathyanarayana

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10115

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      The copolymerization of methyl methacrylate and vinyl acetate under high oxygen pressure was investigated. The copolyperoxide compositions obtained from 1H and 13C NMR spectra led to the determination of the reactivity ratios. The reactivity ratios indicated a larger proportion of MMA units statistically placed in the copolyperoxides. The copolyperoxides showed highly exothermic degradation. The activation energy of thermal degradation suggested that degradation was controlled by the dissociation of the peroxide ([BOND]O[BOND]O[BOND]) bonds of the copolyperoxide chain.

    14. Radical polymerization of vinyl thiocyanatoacetate: Participation of group-transfer mechanism (pages 573–582)

      Tsuneyuki Sato, Hidekazu Mukuno, Hirotaka Ishida, Makiko Seno and Tomohiro Hirano

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10137

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      Vinyl thiocyanatoacetate (VTCA) showed high radical polymerizability analogously to vinyl acetate. The radical polymerization of VTCA involved significant chain transfer to the monomer that limited the molecular weight of the resulting polymer (chain-transfer constant = 9.6 × 10−3 at 60 °C). The polymerization proceeded through normal vinyl addition and intramolecular transfer of the cyano group to yield poly (VTCA) partly containing ester and thioether linkages in the main chain. The cyano group transfer became progressively more important with decreasing monomer concentration.

    15. Investigations of thermal polymerization in the stable free-radical polymerization of 2-vinylnaphthalene (pages 583–590)

      Jeremy R. Lizotte, Brian M. Erwin, Ralph H. Colby and Timothy E. Long

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10131

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      The feasibility of utilizing stable free-radical polymerization (SFRP) in the synthesis of well-defined poly(2-vinylnaphthalene) homopolymers has been investigated. Efforts to control molecular weight by manipulating the initiator concentration while maintaining a 2,2,6,6-tetramethylpiperidinyl-1-oxy:benzoyl peroxide molar ratio of 1.2:1 proved unsuccessful. In situ Fourier transform infrared spectroscopy indicated that the rate of monomer disappearance under SFRP and thermal conditions was identical. A kinetic analysis of the thermal polymerization of styrene and 2-vinylnaphthalene suggested that the additional fused ring in 2-vinylnaphthalene increased the propensity for thermal polymerization.

    16. Synthesis of proton-conducting membranes by the utilization of preirradiation grafting and atom transfer radical polymerization techniques (pages 591–600)

      Svante Holmberg, Peter Holmlund, Carl-Eric Wilén, Tanja Kallio, Göran Sundholm and Franciska Sundholm

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10146

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      The atom transfer radical polymerization (ATRP) of styrene onto poly(vinylidene fluoride)-graft-poly(vinylbenzyl chloride) (PVDF-g-PVBC) membranes is reported. Novel membranes were designed for fuel-cell applications. The benzyl chloride groups in the PVDF-g-PVBC membranes functioned as initiators, and a Cu(n)Xn/ligand (where X is Cl or Br and the ligand is 2,2′-bipyridyl) catalytic system was employed for the ATRP. The membranes became proton-conducting after sulfonation of the polystyrene (PS) grafts. The highest proton conductivity was 70 mS/cm.

    17. New solvents for cellulose: Hydrazine/thiocyanate salt system (pages 601–611)

      Kazuyuki Hattori, John A. Cuculo and Samuel M. Hudson

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10135

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      The hydrazine/salt system described in the table dissolved cellulose even at room temperature. In this system, a high concentration of salt was necessary to effect the cellulose dissolution; this suggested that an undissociated salt–solvent complex played an important role in the cellulose dissolution. All the cellulose solutions showed liquid crystallinity dependent on the cellulose concentration.

    18. Lanthanocene amide complexes as single-component initiators for the polymerization of (dimethylamino)ethyl methacrylate (pages 612–616)

      Qi Shen, Yaorong Wang, Keda Zhang and Yingming Yao

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10141

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      Polymerization of (dimethylamino)ethyl methacrylate (DMAEMA) by lanthanocene amide complexes was investigated. The results indicated that these complexes are effective initiators for the polymerization of DMAEMA, and the molecular weights of the polymers obtained exceed 100 × 103. The polymerization reactions can be varied over quite a broad range of temperatures from −78 to 40 °C. The central metals and amido groups had a significant effect on the polymerization activity.

    19. Ruthenium-catalyzed fast living radical polymerization of methyl methacrylate: The R[BOND]Cl/Ru(Ind)Cl(PPh3)2/n-Bu2NH initiating system (pages 617–623)

      Shinya Hamasaki, Chie Sawauchi, Masami Kamigaito and Mitsuo Sawamoto

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10148

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      A fast living radical polymerization of methyl methacrylate proceeded with the R[BOND]Cl/Ru(Ind)Cl(PPh3)2 initiating system in the presence of n-Bu2NH as an additive and reached quantitative conversion within 10 h. The number-average molecular weight (Mn) increased in direct proportion to the monomer conversion (up to 105), and the molecular weight distributions were very narrow [weight-average molecular weight/number-average molecular weight (Mw/Mn) ≤ 1.2].

    20. Syntheses and characterizations of poly[2-(dimethylamino)ethyl methacrylate]–poly(propylene oxide)–poly[2-(dimethylamino)ethyl methacrylate] ABA triblock copolymers (pages 624–631)

      Pei-Hong Ni, Qi-Sheng Pan, Liu-Sheng Zha, Chang-Chun Wang, Abdelhamid Elaïssari and Shou-Kuan Fu

      Version of Record online: 4 JAN 2002 | DOI: 10.1002/pola.10144

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      A novel well-defined ABA triblock copolymer PDMAEMA-PPO-PDMAEMA was prepared by oxyanion-initiated polymerization using a telechelic-type potassium alcoholate as initiator. It has been found that the triblock copolymer has very high surface activity and pH/temperature-induced micellization at various aqueous media and temperatures.

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