Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 42 Issue 21

1 November 2004

Volume 42, Issue 21

Pages 5301–5559

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      Thiol–enes: Chemistry of the past with promise for the future (pages 5301–5338)

      Charles E. Hoyle, Tai Yeon Lee and Todd Roper

      Version of Record online: 22 SEP 2004 | DOI: 10.1002/pola.20366

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      The photopolymerization of mixtures of multifunctional thiols and enes is an efficient method for the rapid production of films and thermoset plastics with unprecedented physical and mechanical properties. One of the major obstacles in traditional free-radical photopolymerization is essentially eliminated in thiol–ene polymerizations because the polymerization occurs in air almost as rapidly as in an inert atmosphere. Virtually any type of ene will participate in a free-radical polymerization process with a multifunctional thiol. Hence, it is possible to tailor materials with virtually any combination of properties required for a particular application.

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      Computer modeling of radical copolymerization under unusual conditions (pages 5339–5353)

      Alexei R. Khokhlov, Anatoly V. Berezkin and Pavel G. Khalatur

      Version of Record online: 16 SEP 2004 | DOI: 10.1002/pola.20451

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      A survey is given of a recently developed approach, called conformation-dependent sequence design, as applied to computer-aided design of nontrivial chemical sequences in copolymers obtained via heterogeneous radical polymerization. We outline several new synthetic strategies under unusual conditions, leading to binary quasirandom copolymers with large-scale compositional inhomogeneity, long-range correlated and gradient distribution of monomeric units along the chain.

  3. Articles

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    1. Fluoropolyethers end-capped by polar functional groups. IV. A novel approach to the evaluation of reactivities of hydroxy-terminated ethoxylated fluoropolyethers in the tin(IV)-catalyzed reactions with isophorone diisocyanate (pages 5354–5371)

      Elena Khomko, Leonid Mashlyakovskiy and Claudio Tonelli

      Version of Record online: 20 SEP 2004 | DOI: 10.1002/pola.20344

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      The effect of catalyst dibutyltin dilaurate (DBTDL) on the kinetics of urethane formation reactions of α,ω-bis(hydroxy)-terminated fluoropolyethers Fomblin® Z-DOL TXs (FPEs) of various molecular weights with isophorone diisocyanate (IPDI) has been studied. Effect of catalyst saturation was revealed for all the reaction systems at higher DBTDL concentrations as well as the appearance of the limiting catalyst concentrations Clim below which the rates of reaction were close to zero. The reaction rate increases significantly with increasing MW of FPE from 776 up to 3405.

    2. Synthesis and characterization of new polystyrenes containing tributyltin moieties linked to the aromatic ring through a methylenic spacer (pages 5372–5383)

      Luigi Angiolini, Daniele Caretti, Laura Mazzocchetti, Elisabetta Salatelli, Rudolph Willem and Monique Biesemans

      Version of Record online: 20 SEP 2004 | DOI: 10.1002/pola.20343

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      Novel polymeric derivatives bearing tributyltin carboxylate moieties in the side chain were synthesized. The coordination at tin in solution and in the solid state was investigated by both Sn-NMR and FT-IR; the metal atom appears completely tetracoordinated in chloroform solution, while in the solid state all polymeric products exhibit both tetra- and pentacoordination at tin, the latter increasing with the amount of tin containing units. No evidence of tin leaching by hydrolysis of the organometallic ester was observed for these materials.

    3. Stereocontrolled anionic alternating copolymerization of ethylphenylketene with benzaldehyde by a bisoxazoline ligand (pages 5384–5388)

      Daisuke Nagai, Atsushi Sudo and Takeshi Endo

      Version of Record online: 16 SEP 2004 | DOI: 10.1002/pola.20310

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      Anionic copolymerization of ethylphenylketene with benzaldehyde, using butyllithium or diethylzinc as the initiator, proceeded in a perfect 1:1 alternating manner to produce the corresponding polyester that had a repeating unit with two adjacent chiral centers. The relative stereochemistry between these two chiral centers was successfully controlled by the addition of (S,S)-(-)-2,2′-isopropylidenebis(4-tert-butyl-2-oxazoline), producing the corresponding polyester with excellent diastereoselectivity (erythro-configuration:threo-configuration = 4:96).

    4. Strategies toward biocompatible artificial implants: Grafting of functionalized poly(ethylene glycol)s to poly(ethylene terephthalate) surfaces (pages 5389–5400)

      Ryoko Fukai, Piwai H. R. Dakwa and Wei Chen

      Version of Record online: 20 SEP 2004 | DOI: 10.1002/pola.20352

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      Epoxide and aldehyde end-functionalized poly(ethylene glycol)s were grafted to poly(ethylene terephthalate) film substrates that contained amine or alcohol groups. Protein adsorption was carried out using collagen, lysozyme, and albumin. After PEG grafting, the amount of protein adsorbed was reduced in all cases. Surface requirements for protein resistance are: surfaces with longer PEG chains and higher chain density, especially the former, are more protein resistant, PEG grafted to surfaces containing branched or network polymers is not effective at covering the underlying substrate thus does not protect the entire surface from protein adsorption, and substrates containing surface charge are less protein-resistant.

  4. Rapid Communications

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    1. Sequence-controlled ethylene/vinyl cinnamate copolymers: Synthesis and application to the photoalignment of liquid crystals (pages 5401–5406)

      Ji-Heum Yoo, Iwhan Cho and Sang Youl Kim

      Version of Record online: 20 SEP 2004 | DOI: 10.1002/pola.20433

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      A sequence-controlled copolymer of ethylene (3) and vinyl cinnamate [1; i.e., poly(1-cinnamoyloxyoctamethylene) (sc-PEVC)] was prepared by the reaction of poly(1-hydroxyoctamethylene) with cinnamoyl chloride. The resulting polymer (weight-average molecular weight > 100,000) exhibited a glass-transition temperature at 16 °C. Liquid-crystal cells were constructed via the sandwiching of nematic liquid crystals between a pair of glass plates coated with sc-PEVC. The irradiation of the cells with linearly polarized ultraviolet light produced a parallel alignment of liquid crystals to the polarization direction of ultraviolet light; there was excellent alignment stability even at higher temperatures (150 and 200 °C). This unexpected high temperature stability was attributed to the formation of a network structure resulting from exclusive interchain crosslinking. The pretilt angle of the parallel aligned liquid crystals was notably high (3.05°).

    2. Novel anionic thermally latent initiating systems: Anionic polymerization of glycidyl phenyl ether with potassium tert-butoxide/active methylene compounds (pages 5407–5412)

      Tetsuo Hino and Takeshi Endo

      Version of Record online: 20 SEP 2004 | DOI: 10.1002/pola.20435

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      Novel thermally latent initiators were prepared in situ by the treatment of potassium tert-butoxide (tBuOK) with several active methylene compounds: diethyl malonate (1a), acetylacetone (1b), ethyl acetoacetate (1c), and ethyl phenylacetate (1d). Their activities for a thermally latent initiating system were examined in the polymerization of glycidyl phenyl ether (2 or GPE), and these tBuOK/1a1d systems were found to serve as anionic thermally latent initiators. The activity order for the initiator was estimated as follows: tBuOK/1b ≫ tBuOK/1d > tBuOK/1a ≈ tBuOK/1c.

  5. Articles

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    1. Photochemical attachment of polymers on planar surfaces with a covalently anchored monolayer of a novel naphthyl ketone photochemical radical generator (pages 5413–5423)

      K. Dayananda, R. Dhamodharan, K. Vijayakumaran and T. Rajamannar

      Version of Record online: 16 SEP 2004 | DOI: 10.1002/pola.20345

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      A monolayer of covalently anchored, novel, binaphthyl ketone is used as a surface-confined photochemical radical generator for anchoring a variety of polymers to silicon surfaces. The precursor surface-confined photochemical radical generator is synthesized by the application of a facile and novel method for the oxidation of sterically hindered benzylic hydrocarbons to carbonyl compounds. The covalently attached monolayers are characterized by X-ray photoelectron spectroscopy, ellipsometry, and water contact angle measurements. The method developed is applicable to the preparation of a monolayer of a variety of polymers on a wide range of substrates carrying surface hydroxyl groups.

    2. Synthesis and properties of new aromatic polyimides based on 2,5-bis(4-amino-2-trifluoromethylphenoxy)-tert-butylbenzene and various aromatic dianhydrides (pages 5424–5438)

      Chin-Ping Yang, Yu-Yang Su and Kuen-Lin Wu

      Version of Record online: 22 SEP 2004 | DOI: 10.1002/pola.20313

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      A novel, fluorinated diamine monomer, 2,5-bis(4-amino-2- trifluoromethylphenoxy)-tert-butylbenzene (II) was synthesized through the nucleophilic substitution reaction of tert-butylhydroquinone (t-BHQ) and 2-chloro-5-nitrobenzotrifluoride, giving 2,5-Bis(4-nitro-2-trifluoromethylphenoxy)-tert-butylbenzene (I), followed by catalytic reduction. A series of PI V were synthesized from II with various aromatic dianhydrides (IIIa–f) in a two-stage process with the thermal imidization of poly(amic acid). The resulting V series exhibit lighter color, better solubility, and lower dielectric constants and moisture absorption than the corresponding nonfluorinated VII series. The V Series were characterized by good mechanical and thermal property.

    3. Unexpected end-groups of poly(acrylic acid) prepared by RAFT polymerization (pages 5439–5462)

      Marie-France Llauro, Julien Loiseau, Fernande Boisson, Frédéric Delolme, Catherine Ladavière and J. Claverie

      Version of Record online: 22 SEP 2004 | DOI: 10.1002/pola.20408

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      Low-molecular-weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization. The PAA end-groups of the polymer were analyzed before and after neutralization by sodium hydroxide. Chains terminated by the expected thiol were in smaller quantities than those terminated by an H atom or by a thiolactone.

    4. Synthesis and characterization of polyurethane anionomers with bisazoaromatic chromophores and carboxylate groups (pages 5463–5470)

      Tinca Buruiana and Emil C. Buruiana

      Version of Record online: 16 SEP 2004 | DOI: 10.1002/pola.20370

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      Novel polyurethane anionomers containing carboxylate groups and azoaromatic chromophores introduced by means of 2-[(2-hydroxyethyl)(4-{4-(phenyldiazenyl)phenyl} diazenyl)phenyl]aminoethanol were synthesized and characterized. Photobehavior of the polymers in the solution and thin film showed that under UV irradiation (γ = 365 nm) all anionomers present a photo-response depending on the structural and electrostatic factors. The red shifts in the absorption spectra suggest the formation of H-aggregates.

    5. Influence of the type of epoxy hardener on the structure and properties of interpenetrated vinyl ester/epoxy resins (pages 5471–5481)

      O. Gryshchuk and J. Karger-Kocsis

      Version of Record online: 16 SEP 2004 | DOI: 10.1002/pola.20371

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      The morphology – toughness relationship of vinylester/cycloaliphatic epoxy (VE/EP) hybrid resins of interpenetrating network (IPN) structure was studied as a function of EP hardening. EP was crosslinked with diamines, using a borontrifluoride complex and by adding maleic anhydride. The latter favored the formation of a grafted IPN structure. IPN was characterized by the width of the entangling bands and surface roughness parameters deduced from atomic force microscopic (AFM) scans taken on ion-etched surfaces. Toughness was described by the fracture toughness (Kc) and energy (Gc), the values of which increased with increasing maximum roughness depth (Rmax) as displayed.

    6. Synthesis of poly(L-lactide)-grafted pullulan through coupling reaction between amino group end-capped poly(L-lactide) and carboxymethyl pullulan and its aggregation behavior in water (pages 5482–5487)

      Tatsuro Ouchi, Tetsuji Minari and Yuichi Ohya

      Version of Record online: 22 SEP 2004 | DOI: 10.1002/pola.20336

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      Poly(L-lactide) (PLLA)-grafted pullulan (Pul-g-PLLA), consisting of a hydrophilic carboxymethyl Pul (CM-Pul) main chain and hydrophobic PLLA graft chains, was synthesized through a direct coupling reaction between amino group end-capped PLLA (PLLA-NH2) and CM-Pul using 2-ethoxy-1-(ethoxycarbonyl)-1,2-dihydroquinoline as a condensation reagent. Graft copolymer Pul-g-PLLAs with different graft numbers and graft chains were obtained. Pul-g-PLLAs with over 78 wt % sugar unit content were found to form unimodal self-aggregates (39–100 nm) in water.

    7. Synthesis and thermal and spectroscopic properties of macrocyclic vinyl aromatic polymers (pages 5488–5503)

      Rong Chen, Gennadi G. Nossarev and Thieo E. Hogen-Esch

      Version of Record online: 24 SEP 2004 | DOI: 10.1002/pola.20413

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      Macrocyclic poly(9,9-dimethyl-2-vinylfluorene) and poly(2-vinylnaphthalene) have been synthesized through anionic polymerization and high-dilution coupling and have been characterized with nuclear magnetic resonance, matrix-assisted laser desorption/ionization, and size exclusion chromatography. The glass-transition temperatures of the cycles are much higher than those of the matching linear polymers. Ultraviolet–visible spectroscopy shows variations attributable to intensity borrowing. The cycles, in agreement with previous emission data on the polystyrene cycles, show stronger emissions than the matching linear polymers.

    8. Hyperbranched-polyethyleneiminated functional polymers. III. Synthesizing thiophosphate-containing pseudodendritic poly-ethyleneiminated polyoxypropylenediamine and its behavior at an oil/metal interface under extreme pressure (pages 5504–5513)

      Ping-Lin Kuo and Sheng-Chung Ni

      Version of Record online: 24 SEP 2004 | DOI: 10.1002/pola.20400

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      A simple synthetic route for preparing a thiophosphate-containing pseudo-dendritic polyethyleneiminated polyoxypropylenediamine D400(EI)xP is presented. The number of ethyleneimine group (EI) in D400(EI)xP were determined by 1H- and 13C-NMR to be 4.3 for D400(EI)4P and 8.9 for D400(EI)8P and the extent of branch was quantitatively determined using potentiometric titration. The numbers of thiophosphate groups per thiophosphate-containing pseudo-dendritic polymers molecule for D400(EI)0P, D400(EI)4P and D400(EI)8P were calculated by elemental analyses of sulfur content. The AW performance of these synthesized thiophosphate-containing pseudo-dendritic polymers was examined by measuring the temperature of oil, and the frictional coefficient and electrical contact resistance between the two metal surfaces. More thiophosphate groups on the either sides of D400(EI)8P are found to increase the electrical contact resistance due to the chemical adsorption of thiophosphate groups onto metal surfaces, forming a thick layer and reducing operating time required to form the adsorption layer. Interestingly, the adsorption layers markedly reduce the frictional coefficient (∼0.012) and limit the increase in oil temperature (∼90 °C) throughout the entire period of AW test, reducing weight loss of the metal (0.1 mg).

    9. Synthesis and thermal crosslinking of benzophenone-modified poly(dimethylsiloxane)s (pages 5514–5522)

      Joseph M. Mabry and William P. Weber

      Version of Record online: 24 SEP 2004 | DOI: 10.1002/pola.20410

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      [Ph3P]3RuH2CO catalyzes the anti-Markovnikov addition of an ortho C[BOND]H bond of benzophenone across the C[BOND]C double bonds of α,ω-bis(trimethylsilyloxy)copoly(dimethylsiloxane/vinylmethylsi loxane) (99:1), α,ω-bis(vinyldimethylsilyloxy)poly(dimethylsiloxane), and 1,3-divinyltetramethyldisiloxane. Their molecular weights increase with heating to 300 °C for 1 h. Crosslinking may occur through the pyrocondensation of pendant anthracene groups produced by the pyrolysis of the attached ortho-alkyl benzophenones.

    10. Synthesis and characterization of well-defined poly(2-hydroxyethyl methacrylate-co-styrene)-graft-poly(ε-caprolactone) by sequential controlled polymerization (pages 5523–5529)

      Xuewei Xu and Junlian Huang

      Version of Record online: 24 SEP 2004 | DOI: 10.1002/pola.20387

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      A new graft copolymer poly(2-hydroxyethyl methacrylate-co-styrene) -graft-poly(ϵ-caprolactone) was successfully prepared by combination of reversible addition-fragmentation chain transfer polymerization (RAFT) with ring-opening polymerization (ROP). The copolymerization of St and HEMA and then grafted polymerization of ϵ-CL were controllable. It was confirmed that in our system all hydroxyl groups of P(HEMA-co-St) took part in the initiation, and the grafted efficiency of ϵ-CL was very high.

    11. Effect of solvent quality on kinetics of tethered layer formation (pages 5530–5537)

      Heqing Huang, Erin C. Fulchiero and Lynn S. Penn

      Version of Record online: 24 SEP 2004 | DOI: 10.1002/pola.20407

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      We conducted a study of the effect of solvent quality on the kinetics of formation of a layer of polymer chains tethered to a solid substrate. All experimental variables were held constant except for the χ-parameter between the polymer and solvent. The density of the tethered layer increased with the χ-parameter, but the time to completion of the layer was not affected.

    12. Regiocontrolled synthesis of poly(3-alkylthiophene)s by Grignard metathesis (pages 5538–5547)

      Yuxia Mao, Yu Wang and Brett L. Lucht

      Version of Record online: 24 SEP 2004 | DOI: 10.1002/pola.20375

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      As shown in Fig. 4 Poly(3-octadecylthiophene)s (P3OTs) were prepared via Grignard metathesis polymerization of 2,5-dibromo-3-octadecylthiophene in the presence of palladium and nickel catalysts. Polymerizations at higher temperature with nickel catalysts are regioregular, while polymerizations at lower temperature with palladium catalysts are regiorandom. P3OTs with higher regioregularity have longer wavelength visible absorptions, while P3OTs with lower regioregularity have shorter wavelength absorptions.

    13. Kinetic analysis of styrene atom transfer radical polymerization: Extraction of radical-radical termination rate coefficients (pages 5548–5558)

      Devon A. Shipp and Xiang Yu

      Version of Record online: 24 SEP 2004 | DOI: 10.1002/pola.20396

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      Kinetic studies of the atom transfer radical polymerization (ATRP) of styrene are reported, with the particular aim of determining radical-radical termination rate coefficients (<kt>). The reactions are analyzed using the persistent radical effect (PRE) model. Using this model, average radical-radical termination rate coefficients are evaluated. Under appropriate ATRP catalyst concentrations, <kt> values of approximately 2 × 108 L mol−1 s−1 at 110 °C in 50 vol % anisole were determined.

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