Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 1

1 January 2005

Volume 43, Issue 1

Pages 1–233

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      Biological–synthetic hybrid block copolymers: Combining the best from two worlds (pages 1–17)

      Harm-Anton Klok

      Version of Record online: 11 NOV 2004 | DOI: 10.1002/pola.20527

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      Biological–synthetic hybrid block copolymers are an interesting class of materials that can synergetically combine the properties of the individual components and overcome several of their limitations. This article specifically focuses on protein/peptide–synthetic hybrid block copolymers. Both synthetic methodologies used to site-selectively conjugate proteins or peptides and synthetic polymers and the properties and potential applications of these materials are discussed.

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    1. Synthesis and characterization of N-vinylpyrrolidone-tert-butyl methacrylate-methacrylic acid terpolymers having amino sugar or bioactive amino side compounds (pages 18–27)

      Gerardo Martínez, Marta Fernández-García and Manuel Sánchez-Chaves

      Version of Record online: 11 NOV 2004 | DOI: 10.1002/pola.20347

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      Chemical reactions through the use of carboxylic acid groups were satisfactorily carried out on N-vinylpyrrolidone-tert-butyl methacrylate copolymers partially functionalized with acidic groups, with amino sugar (2-amino-2-deoxy-D-glucose (glucosamine)) or model bioactive amino compounds (benzocaine, phenethylamine, tyramine).

    2. Solution proprieties of dendritic triazine/poly(ethylene glycol)/dendritic triazine block copolymers (pages 28–41)

      Hassan Namazi and Mohsen Adeli

      Version of Record online: 11 NOV 2004 | DOI: 10.1002/pola.20471

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      Dendritic–linear–dendritic triblock copolymers based on poly(ethylene glycol) (PEG) as the core and dendritic triazine blocks were synthesized. The micellar and aggregation characteristics of the compounds were investigated with NMR and fluorescence spectroscopy. The NMR investigations were carried out in a variety of solvents and they show the aggregation behavior of the block copolymers with extended or packed conformation of PEG in the solvents, as previously observed in similar systems. Also, fluorescence investigations of some of the isolated compounds in aqueous solutions displayed micellar behavior. The critical micelle concentrations of the copolymers were determined with a fluorescence technique.

    3. Rate enhancement for nitroxide stable free radical polymerization of n-butyl acrylate by dodecylbenzenesulfonic acid (pages 42–49)

      Kuo-Chung Cheng, Jiun-Jeng Chen, Wen-Yen Chiu, Lee Yih Wang and Ping-Chieh Wang

      Version of Record online: 11 NOV 2004 | DOI: 10.1002/pola.20398

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      DDBSA, was chosen as a new rate-accelerating additive for 2,2,6,6,-teramethyl-1-piperidinyloxy (TEMPO)-mediated stable free radical polymerization of n-butyl acrylate (n-BA) monomers with 2,2′-azobisisobutyronitrile (AIBN). It was found that the number-average molecular weight of polymers could reach about ten thousand with a narrow polydispersity index (PDI) of 1.4 in a few minutes, which was faster than other systems reported previously. But, at higher conversion, the molecular weight distribution of polymers became broad, and a bimodal distribution occurred. The macro-initiators isolated from the former polymers with narrow PDI could be extended by polymerization with monomers by the addition of DDBSA.

    4. Hydrogen-bond-assisted stereocontrol in the radical polymerization of N-isopropylacrylamide with primary alkyl phosphate: The effect of the chain length of the straight ester group (pages 50–62)

      Tomohiro Hirano, Satoshi Ishii, Hiroko Kitajima, Makiko Seno and Tsuneyuki Sato

      Version of Record online: 15 NOV 2004 | DOI: 10.1002/pola.20475

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      Radical polymerizations of N-isopropylacrylamide (NIPAAm) in the presence of primary alkyl phosphates were investigated. Syndiotactically rich poly(NIPAAm)s were obtained from −60 to 0°C, whereas isotactically rich poly(NIPAAm)s were obtained by lowering the temperature to −80°C. Job's plots for mixtures of NIPAAm and tri-n-butyl phosphate (TBP) revealed that NIPAAm and TBP formed a 1:1 complex at 0°C and a predominantly 1:2 complex at −80°C through a hydrogen-bonding interaction. Therefore, the stereospecificity of NIPAAm polymerization should depend on the stoichiometry of the hydrogen-bond-assisted complex. The mechanism for this polymerization system was discussed.

    5. Synthesis of nanocylinders consisting of graft block copolymers by the photo-induced ATRP technique (pages 63–70)

      Koji Ishizu and Hirokazu Kakinuma

      Version of Record online: 11 NOV 2004 | DOI: 10.1002/pola.20491

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      The well-defined poly(t-butyl methacrylate) cylinders: PSD-graft-PBMA (PBMA-C) were prepared by grafting from photoinduced ATRP of BMA initiated by multifunctional polystyrene (PSD) having N,N-diethyldithiocarbamate (DC) pendant groups in the presence of CuCl/bpy under UV irradiation. A complex, CuCl/bpy reversibly activated the dormant polymer chains via a DC transfer such as Cu(DC)Cl/bpy. Subsequently, the nanocylinders consisting of graft block copolymers [PSD-graft-(PBMA-block-PMMA) and PSD-graft-(PBMA-block-PS)] were prepared by similar photoinduced ATRP with PBMA-C precursor as a polyinitiator with the controlled/living radical mechanism.

    6. Atom transfer radical polymerization of cyclohexyl methacrylate at a low temperature (pages 71–77)

      Alexandra Muñoz-Bonilla, Enrique López Madruga and Marta Fernández-García

      Version of Record online: 18 NOV 2004 | DOI: 10.1002/pola.20489

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      The atom transfer radical polymerization of cyclohexyl methacrylate (CHMA) at a low temperature is reported. Controlled polymerizations were obtained with a monofunctional initiator in bulk and in toluene, diphenyl ether, and benzonitrile solutions. Moreover, polymerizations of CHMA were conducted in toluene solutions with two different difunctional initiators. All the reactions yielded polymers with molecular weights similar to the predicted ones and low molecular weight distributions. The living character of the different polymers was confirmed by the preparation of well-defined diblock and triblock copolymers.

    7. Synthesis and polymerization of new self-polymerizable quinoxaline monomers (pages 78–91)

      Jong-Beom Baek and Frank W. Harris

      Version of Record online: 15 NOV 2004 | DOI: 10.1002/pola.20476

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      A design and synthesis of new self-polymerizable phenylquinoxaline monomer mixtures were studied to improve both the reactivity of monomers for aromatic nucleophilic substitution and the flexibility of resulting polymers. The thin films of new polymers displayed excellent room-temperature tensile properties such as strength, modulus, elongation, and toughness. The melt viscosity of polymer linearly decreased as frequency increased displaying great shear thinning effect for good processability.

    8. Poly(butylene terephthalate-co-5-tert-butyl isophthalate) copolyesters: Synthesis, characterization, and properties (pages 92–100)

      Francisco Gómez, Robert Quintana, Antxon Martñez De Ilarduya, Elisabet Rudé and Sebastián Muñoz-Guerra

      Version of Record online: 18 NOV 2004 | DOI: 10.1002/pola.20477

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      The effect exerted by the insertion of 5-tert-butyl isophthalate units on thermal, tensile, and gas transport properties of PBT was evaluated. Both Tm and crystallinity were found to decrease steadily with copolymerization whereas Tg increased. Permeability and solubility also increased with the content in substituted isophthalic units. The homopolyester poly(5-tert-butyl isophthalate) clearly deviated from this trend suggesting the occurrence of a different structure in the solid state.

    9. 1,5-Diphenyl-1,4-diyn-3-one: A highly efficient photoinitiator (pages 101–111)

      Robert Liska and Bernhard Seidl

      Version of Record online: 18 NOV 2004 | DOI: 10.1002/pola.20484

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      In a continuation of our research on new chromophores for photoinitiators (PIs), we investigated a triple-bond-containing benzophenone derivative. 1,5-Diphenyl-1,4-pentadiyn-3-one (2) was prepared from phenylacetylene and ethyl formate by a one-pot reaction. Differential scanning photocalorimetry experiments in lauryl acrylate of 2 showed surprisingly high activity for the double-bond conversion and rate of polymerization at the lowest PI concentrations and even without any coinitiator. By the application of monomers with abstractable hydrogens, significant improvement in the photoreactivity was observed. Ultraviolet–visible spectroscopy revealed strong absorption up to 350 nm. Steady-state photolysis experiments proved that the photochemistry of this compound was faster than that of benzophenone.

    10. Synthesis, characterization, and water sorption properties of new aromatic polyamides containing benzimidazole and ethylene oxide moieties (pages 112–121)

      Vanesa Ayala, Eva M. Maya, Jose M. García, Jose G. De La Campa, Angel E. Lozano and Javier De Abajo

      Version of Record online: 19 NOV 2004 | DOI: 10.1002/pola.20486

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      New amorphous polyamides, containing a benzimidazole side group and ethylene oxide moieties in the structural repeat unit, were synthesized by low temperature polycondensation. The aim of this design was to obtain polyamides more soluble in common organic solvents, and hence with better processability than benzimidazole-polyamides, while maintaining the water sorption properties characteristic of the latter.

    11. Synthesis of new amphiphilic and lypophilic polymer networks containing 2-methyl- and 2-nonyl-2-oxazoline by the macroinitiator method (pages 122–128)

      Juan Carlos Rueda, Hartmut Komber and Brigitte Voit

      Version of Record online: 19 NOV 2004 | DOI: 10.1002/pola.20492

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      New amphiphilic and lypophilic polymer networks were synthesized by the cationic ring-opening copolymerization of 2-methyl-2-oxazoline and/or 2-nonyl-2-oxazoline and 2,2′-tetramethylenebis(2-oxazoline), respectively, with random copolymers of chloromethylstyrene and methyl methacrylate or of chloromethylstyrene and styrene as macroinitiators. The absorption of polar solvents by the amphigels depends of the molar ratio of 2-methyl- to 2-nonyl-2-oxazoline inside the polymer network favoring the absorption of polar solvents with a higher content of 2-methyl-2-oxazoline. The hydrogel structures were characterized by high-resolution magic angle spinning (HRMAS) NMR spectroscopy. The determined heterogeneous gel structure corresponds well with the observed solvent swelling behavior.

    12. Synthesis and solution properties of poly(methacrylate)s with semipolar structures on the side chains (pages 129–141)

      Tomoaki Hiwatashi, Kazuhide Hayama, Yoshiaki Sawada and Takahito Itoh

      Version of Record online: 22 NOV 2004 | DOI: 10.1002/pola.20485

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      Three charged polymers—poly[N,N-dimethyl-N-(2-methacryloyloxyethyl)amine N-oxide] [poly(DMANO)], poly[N-ethyl-N,N-dimethyl-N-(2-methacryloyloxyethyl)ammonium ethyl sulfate] [poly(EDMES)],and poly[N,N-dimethyl-N-(2-methacryloyloxy)ethylammonioacetate] [poly(DMEAA)]—were prepared by the reaction of poly[2-(N,N-dimethylamino)ethyl methacrylate] with hydrogen peroxide, chloroacetic acid, and diethyl sulfate, respectively. Poly(EDMES) showed typical polyelectrolyte behavior, but the other two polymers [poly(DMANO) and poly(DMEAA)] exhibited antipolyelectrolyte behavior.

    13. Copolymerization kinetics of N-isopropylacrylamide and diethylene glycol monomethylether monomethacrylate determined by online NMR spectroscopy (pages 142–148)

      Stefan Gramm, Hartmut Komber and Dirk Schmaljohann

      Version of Record online: 22 NOV 2004 | DOI: 10.1002/pola.20514

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      The kinetics of the copolymerization of N-isopropylacrylamide (NiPAAm) and diethylene glycol monomethylether monomethacrylate were followed by on–line 1H NMR spectroscopy. Two copolymerization reactions were sufficient to evaluate the kinetic data with the Extended-Kelen–Tüdös method as well as the nonlinear least square method. The copolymerization parameters were determined as rNiPAAm = 0.70 and rDEGMA = 2.0. The higher reactivity of the methacrylate compared to the NiPAAm is in good agreement with other kinetic data of similar systems.

    14. Synthesis of photosensitive and thermosetting poly(phenylene ether) based on poly[2,6-di(3-methyl-2-butenyl)phenol-co-2,6-dimethyl-phenol] and a photoacid generator (pages 149–156)

      Kazuya Matsumoto, Yuji Shibasaki, Shinji Ando and Mitsuru Ueda

      Version of Record online: 22 NOV 2004 | DOI: 10.1002/pola.20490

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      A chemically amplified photosensitive and thermosetting polymer based on poly[2,6-di(3-methyl-2-butenyl)phenol(20 mol %)-co-2,6-dimethylphenol(80 mol %)] and a photoacid generator (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile (PTMA) has been developed. Crosslinking reactions of copolymers were carried out by the thermal treatment at 300 °C for 1 h under nitrogen. The glass-transition temperatures of the cured copolymers reached around 300 °C in nitrogen. The dielectric constant of the cured copolymer film was 2.6 estimated from the refractive index. A fine negative image featuring 8-micrometer line-and-space patterns was obtained on a film exposed to 100 mJ cm−2 with 436 nm light in the contact-printed mode.

    15. Synthesis, characterization, thermal properties, and antimicrobial activity of 4-chloro-3-methyl phenyl methacrylate/8-quinolinyl methacrylate copolymers (pages 157–167)

      Milan V. Patel, Jatin N. Patel, Arabinda Ray and Rajni M. Patel

      Version of Record online: 22 NOV 2004 | DOI: 10.1002/pola.20488

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      4-Chloro-3-methyl phenyl methacrylate (CMPM) and 8-quinolinyl methacrylate (8-QMA) were synthesized and characterized with IR and 1H NMR techniques. The poly(CMPM-co-8-QMA) homopolymers and copolymers with different compositions were prepared by free-radical polymerization with azobisisobutyronitrile as the initiator at 70 °C. The copolymers were characterized with IR spectroscopy and gel permeation chromatography. UV spectroscopy was used to obtain the copolymer compositions, which were used to calculate the reactivity ratios with the Fineman–Ross linearization method. The thermal stability and activation energy for the decomposition of the polymers were obtained from thermogravimetric analysis data. The homopolymers and copolymers were tested for their antimicrobial activity against bacteria, fungi, and yeast.

    16. Synthesis, characterization, and application of melamine-based dendrimers supported on silica gel (pages 168–177)

      Erick J. Acosta, Sergio O. Gonzalez and Eric E. Simanek

      Version of Record online: 22 NOV 2004 | DOI: 10.1002/pola.20493

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      Dendrimers supported on silica gel were prepared using convergent and divergent approaches. The materials that result are different as determined by surface analysis techniques, notably TGA, and mass spectrometry of samples derived upon degradation of the support. Composite materials showed increasing sequestration of the monochlorotriazine herbicide atrazine with increasing generation. Materials prepared by the divergent pathway sequestered more atrazine than materials prepared convergently.

    17. Evolution of the termination rate coefficient in styrene polymerization (pages 178–187)

      José Antonio Arcos-Casarrubias, Roberto Olayo and Jaime Noriega Bernechea

      Version of Record online: 22 NOV 2004 | DOI: 10.1002/pola.20497

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      Styrene bulk polymerization was conducted at 70 °C with high initiator concentration. The overall termination rate coefficient was found independent of conversion in the dilute regime, as observed from cumulative MWDs. The figure shows the relative decrease in normalized termination rate coefficients as a function of conversion and the full line represents the ratio of diffusion coefficients, the influence of the translational diffusion initiates at the semidiluted regime.

    18. Poly(ether ketone)–polyisobutylene block copolymers: Synthesis and phase behavior (pages 188–202)

      Wolfgang H. Binder and Doris Machl

      Version of Record online: 22 NOV 2004 | DOI: 10.1002/pola.20483

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      Telechelic poly(ether ketone)s (PEKs) and polyisobutylenes (PIBs) were combined to form PIB[BOND]PEK[BOND]PIB triblock copolymers and (PIB[BOND]PEK)n multiblock copolymers via the formation of urea linkages. Monovalent and bivalent amino telechelic PIBs were prepared quantitatively from allyl telechelic PIBs by a newly developed reaction sequence featuring nucleophilic reaction steps. Telechelic PEK[BOND]NCO polymers were prepared from the corresponding amino telechelic PEKs via a reaction with diphosgene. The highly reactive PEK[BOND]NCO and PIB[BOND]NH2 telechelics formed PEK[BOND]PIB block copolymers only quantitatively when appropriately reactive primary amino groups were present on the amino telechelic PIBs. The obtained block copolymers were microphase-separated and featured mostly lamellar structures, as determined by small-angle X-ray scattering (SAXS). Temperature-dependent SAXS measurements revealed ordered polymers in the melt up to 210 °C.

    19. Microemulsion copolymerization of styrene and acrylonitrile with n-butanol as the cosurfactant (pages 203–216)

      Yuanchang Shi, Youshi Wu, Jingcheng Hao and Ganzuo Li

      Version of Record online: 22 NOV 2004 | DOI: 10.1002/pola.20495

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      The microemulsion copolymerization of styrene and acrylonitrile in an n-butanol/cetyltrimethylammonium bromide/oil/water microemulsion system was studied. The solubilization sites of the two monomers were determined with an NMR technique. The styrene molecules were solubilized around β-CH2 of cetyltrimethylammonium bromide, and the solubilization was reduced along the hydrocarbon line of the palisade layer. However, acrylonitrile could hardly solubilize in the hydrophobic interior core because of its high polarity. The microemulsion copolymerization of styrene and acrylonitrile was studied with different monomer feed ratios. The mechanism of microemulsion copolymerization for styrene and acrylonitrile was assumed and was supported by the effect of the monomer feed on the conversion, the rate of polymerization, and transmission electron microscopy observations of polymer particles.

    20. Synthesis of acid-sensitive latices by ring-opening metathesis polymerization (pages 217–229)

      Damien Quémener, Valérie Héroguez and Yves Gnanou

      Version of Record online: 22 NOV 2004 | DOI: 10.1002/pola.20513

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      This study describes the synthesis of polynorbornene colloidal partcles able to release active molecules in response to pH change. Such functionalized polynorbornene latices with surface active molecules have been obtained by ring-opening metathesis copolymerization in a dichloromethane/ethanol medium in the presence of an α-norbornenyl poly(ethylene oxide) macromonomer. Two different strategies of introduction of the active molecule—either at their periphery or at their core—have been contemplated. The particles have been characterized by both dynamic light scattering and transmission electron microscopy. Their size was found to range from 260 to 600 nm. The release of the active molecules was monitored by UV spectrometry. After 48 h in an appropriate HCl buffer (pH = 3), more than 80% of the initially linked active molecule was released.

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    1. Controlled radical polymerization of methacrylic acid initiated by diethyldithio-carbamate-mediated iniferter (pages 230–233)

      Koji Ishizu, Hideya Katsuhara and Kazuo Itoya

      Version of Record online: 23 NOV 2004 | DOI: 10.1002/pola.20395

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      Photopolymerizations of methacrylic acid (MA) were carried out in methanol initiated by (4-cyano-4-N,N-diethyldithiocarbamayl)pentanoic acid (CDPA) under UV irradiation. The first-order time-conversion plots showed a straight line. The polydispersities of polymerization products were very narrow (Mw/Mn = 1.21). The Mn of the obtained polymers increased in direct proportion to monomer conversion. The initiator efficiency, (f = 0.92), was close to unity, which indicates that no side reaction occurred. The N,N-diethyldithiocarbamate(DC)-mediated radical mechanism was a dynamic equilibrium that was responsible for the controlled behavior of the polymerization of MA.