Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 45 Issue 11

1 June 2007

Volume 45, Issue 11

Pages 2059–2349

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Notes
    1. You have free access to this content
      Recent advances in the synthesis of well-defined glycopolymers (pages 2059–2072)

      Sebastian G. Spain, Matthew I. Gibson and Neil R. Cameron

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.22106

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      Glycopolymers are receiving increasing interest because of their application in areas such as glycomics, medicine, biotechnology, sensors, and separation science. This review covers recent developments in the synthesis of glycopolymers, with a particular emphasis on (i) the use of controlled radical polymerization to prepare well-defined glycopolymers from unprotected monomers and (ii) post-polymerization modification strategies using reactive polymer precursors (including “click” reactions). Recent work on the production of glycosylated polypeptides, which are under investigation as mimics of naturally occurring glycoproteins, is also included.

  2. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Notes
    1. Polyfluorene presenting dipolar pendent groups and its application to electroluminescent devices (pages 2073–2084)

      Chen-Han Chien, Ping-I Shih, Fang-Iy Wu, Ching-Fong Shu and Yun Chi

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21971

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      Using PF-TPAOXD as the host material doped with 1.5 mol % Os(fppz) allowed us to realize a saturated-red electrophosphorescent device having Commission Internationale de l'Eclairage coordinates of (0.66, 0.34) with a maximum external quantum efficiency of 7.3%. On the other hand, the doped poly(9,9-dioctylfluorene) reference device performed poorly with a maximum external quantum efficiency of 2.6%.

    2. Optically active electrochromism in polyanilines (pages 2085–2090)

      Hiromasa Goto

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21972

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      The electrochemically driven control of the natural optical activity of polyanilines bearing chiral camphorsulfonic acid is reported. Aniline was polymerized in the presence of camphorsulfonic acid by oxidative electrochemical polymerization in water to afford polyanilines containing (+)- or (−)-camphorsulfonic acid. This research elucidated that the polymerization, with cyclic voltammetry scanning up to 1.1 V, produced consistent optically active polyanilines. The polyaniline films thus prepared showed intense and tunable optical activity based on electrochemical reduction/oxidation in a 0.1 M sulfuric acid aqueous solution. The circular dichroism and optical rotation angle of the polymer were tunable by the appropriate adjustment of an externally applied potential as a form of optical modulation.

    3. Synthesis and morphological characterization of poly(ϵ-caprolactone) and poly(2-methyloxazoline) substituted phenyl rings and phenylene oligomers (pages 2091–2104)

      A. Levent Demirel, Seda Yurteri, Ioan Cianga and Yusuf Yagci

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21974

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      Poly(ϵ-caprolactone) (PCL) and Poly(2-methyloxazoline) (POx) substituted poly(phenylene) oligomers were synthesized by cross-coupling of the macromonomers in Yamamato polycondensation reactions. The chemistry of the side chains together with main chain connectivity determine the orientation of the layered poly(phenylene) structures in thin films. Favorable interactions of PCL and POx with the silicon substrate result in layers perpendicular to the substrate. Attachment of a hydrophobic polystyrene (PS) block to the end of PCL stabilizes parallel layers.

    4. Dispersion copolymerization of methyl methacrylate and n-butyl acrylate (pages 2105–2112)

      Sheng Jiang, E. David Sudol, Victoria L. Dimonie and Mohamed S. El-Aasser

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21975

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      Dispersion copolymerizations of methyl methacrylate and n-butyl acrylate produced micrometer-size monodisperse particles with unexpected and obvious core–shell-type morphologies with a hard, methyl methacrylate rich inner core, as shown in the scanning electron micrograph. The comonomer ratio and 2,2′-azobisisobutyronitrile initiator concentration were varied, and the effects on the particle size and molecular weight were determined.

    5. The controlled homogeneous organic solution polymerization of new hydrophilic cationic exo-7-oxanorbornenes via ROMP with RuCl2(PCy3)2CHPh in a novel 2,2,2-trifluoroethanol/methylenechloride solvent mixture (pages 2113–2128)

      David A. Rankin, Steven J. P'Pool, Hans-Jörg Schanz and Andrew B. Lowe

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21976

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      The synthesis and subsequent controlled, homogeneous (co)polymerization of a series of new permanently cationic, hydrophilic exo-7-oxanorbornenes via ROMP is described. (Co)polymerizations were conducted in a novel 2,2,2-trifluoroethanol/methylene chloride solvent mixture employing the first generation Grubbs' catalyst RuCl2(PCy3)2 CHPh. The (co)polymerizations are demonstrated to exhibit all the characteristics of a controlled system facilitating the synthesis of materials with controllable molecular masses and low polydispersity indices. Kinetic differences are observed between monomeric substrates with different halide counterions. The difference is explained in terms of halide exchange reactions occurring at the Ru metal center. Also, two additional halogenated cosolvents were briefly examined.

    6. FTIR/ATR study of the copolymerization of diglycidyl ether of Bisphenol A with methyl-substituted γ-lactones catalyzed by rare earth triflate initiators (pages 2129–2141)

      Mercè Arasa, Xavier Ramis, Josep Maria Salla, Ana Mantecón and Angels Serra

      Article first published online: 13 APR 2007 | DOI: 10.1002/pola.21979

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      Mixtures of DGEBA with γ-valerolactone (γ-VL) or α-methyl-γ-butyrolactone (γ-MBL) 2:1 (mol/mol) were cationically copolymerized in the presence of scandium, ytterbium or lanthanum triflates as initiators. The evolution of the reactive groups was followed by FTIR/ATR spectroscopy. From these experiments we detected the coexistence of two unexpected processes: a reversion of the intermediate spiroorthoester T to the initial products and a depolymerization process, which only takes place in samples with γ-VL with scandium triflate or when the proportion of ytterbium triflate was 3 phr. When γ-MBL was used no depolymerization occurs which support the proposed mechanism.

    7. Flame retardant epoxy resins based on diglycidyl ether of (2,5-dihydroxyphenyl)diphenyl phosphine oxide (pages 2142–2151)

      M. Spontón, J. C. Ronda, M. Galià and V. Cádiz

      Article first published online: 13 APR 2007 | DOI: 10.1002/pola.21980

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      Phosphine oxide-containing epoxy resins were prepared from diglycidyl ether of (2,5-dihydroxyphenyl)diphenyl phosphine oxide (Gly-HPO) and DGEBA by crosslinking with 4,4′-diaminodiphenylmethane (DDM). Several Gly-HPO/DGEBA molar ratios were used to obtain materials with different phosphorus content. The presence of phosphorus increases the LOI values, indicating good flame retardant properties that are related to the formation of a protective phosphorus-rich layer that slowed down the degradation and prevented it from being total.

    8. Preparation of poly(butylene-co-ε-caprolactone carbonate) and their use as drug carriers for a controlled delivery system (pages 2152–2160)

      Yanfei Liu, Kelong Huang, Dongming Peng, Suqin Liu and Hong Wu

      Article first published online: 13 APR 2007 | DOI: 10.1002/pola.21981

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      A novel degradable copolymer, poly(butylene-co-ε-caprolactone carbonate), was synthesized and developed as drug carrier materials. As shown in the above figure, the polymer microcapsules containing a new hydrophilic antibiotic drug pazufloxacin mesilate were elaborated by W/O/W multiple-emulsion method. The results showed that the microcapsules had a spherical, smooth morphology and a diameter of approximately 1 μm. Of all, 87.90% drug encapsulation efficiency has been achieved. The release profiles of pazufloxacin mesilate from microcapsules were found to be biphasic, and had a long release period of over 4 weeks in a pH 7.4 PBS.

    9. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry investigations of polystyrene and poly(methyl methacrylate) produced by monoacylphosphine oxide photoinitiation (pages 2161–2171)

      Faith J. Wyzgoski, Michael J. Polce, Chrys Wesdemiotis and Mark A. Arnould

      Article first published online: 13 APR 2007 | DOI: 10.1002/pola.21982

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      This article reports mechanistic information obtained from photopolymerization with a monoacylphosphine oxide, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, as an initiator, GPC fractionation, and MALDI chain-end characterization of polystyrene and poly(methyl methacrylate). Because the MALDI-TOF spectra for the poly(methyl methacrylate) fractions contained isobaric peaks, poly (methyl-d3 methacrylate-d5), was synthesized, GPC-fractionated, and analyzed by MALDI-TOF MS to obtain spectra with well-resolved peaks for the illustrated structures.

    10. Chemical surface modification of poly(ethylene terephthalate) fibers by aminolysis and grafting of carbohydrates (pages 2172–2183)

      Loïc Bech, Thierry Meylheuc, Bénédicte Lepoittevin and Philippe Roger

      Article first published online: 13 APR 2007 | DOI: 10.1002/pola.21983

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      We describe the synthesis and characterization of glycosylated poly(ethylene terephthalate) fibers. This material is prepared by aminolysis with different diamines followed by reductive amination or amidation with carbohydrates. The surface morphology studies have indicated that the chemical treatment greatly affects the surface of the fibers. This picture obtained by scanning electronic microscopy shows the achieving of a rough surface after reaction with 1,2-diaminoethane (20 min, 50°C).

    11. Synthesis of poly(ester amide)s by the melt polycondensation of semiaromatic polyesters with ethanolamine and their characterization (pages 2184–2193)

      Hatsuhiko Harashina, Toshio Nakane and Takahito Itoh

      Article first published online: 13 APR 2007 | DOI: 10.1002/pola.21984

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      Semiaromatic poly(ester amide)s (PEAs) were synthesized by the melt polycondensation of ethanolamine derivatives with dimethyl terephthalate and ethylene glycol in the presence of tetrabutyl titanate. Interestingly, these PEAs were found to decompose at a lower temperature than poly(ethylene terephthalate). Direct pyrolysis/mass spectrometry suggested that an initial step of the thermal decomposition step was a β-CH hydrogen-transfer reaction via a six-member ring transition state in the ester–ethylene–amide unit that yielded carboxyl and N-vinylamide end groups. The thermal decomposition behavior of PEAs was explained well by semiempirical molecular orbital calculations on the basis of trimer model molecules.

    12. The role of excess nitroxide in the SG1 (N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide)-mediated polymerization of methyl methacrylate (pages 2194–2203)

      Ronan Mchale, Fawaz Aldabbagh and Per B. Zetterlund

      Article first published online: 13 APR 2007 | DOI: 10.1002/pola.21986

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      The use of large Excesses of SG1 in the radical polymerization of methyl methacrylate (MMA) has been shown to lead to significant disproportionation between the nitroxide and propagating radical (PMMA). This is given as reason for lack of control/livingness in SG1-mediated polymerization of MMA

    13. Synthesis and characterization of epoxy resin-montmorillonite nanocomposites obtained by frontal polymerization (pages 2204–2211)

      Alberto Mariani, Simone Bidali, Giuseppe Caria, Orietta Monticelli, Saverio Russo and José María Kenny

      Article first published online: 13 APR 2007 | DOI: 10.1002/pola.21987

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      Frontal Polymerization has been exploited for the preparation of montmorillonite-epoxy resin nanocomposites. This paper compares the latter with those obtained by the classical methods. Frontal Polymerization allows for the obtainment of nanocomposite materials showing characteristics similar or even better than those obtained by the conventional polymerization routes. Moreover, it is characterized by a very easy protocol and reaction times shorter than those typical of the traditional methods.

    14. Atom-transfer radical polymerization of styrene with bifunctional and monofunctional initiators: Experimental and mathematical modeling results (pages 2212–2224)

      Mamdouh Al-Harthi, Long Shun Cheng, João B. P. Soares and Leonardo C. Simon

      Article first published online: 13 APR 2007 | DOI: 10.1002/pola.21988

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      We compared the atom transfer radical polymerization of styrene with benzal bromide (bifunctional initiator) and 1-bromoethyl benzene (monofunctional initiator), and used a Monte Carlo model to predict polymerization rates and the development of the molecular weight distribution (MWD). The figure shows the MWD predicted for styrene polymerization with benzal bromide at 110 °C for several polymerization times.

    15. ABA-type amphiphilic triblock copolymers containing p-ethoxy azobenzene via atom transfer radical polymerization: Synthesis, characterization, and properties (pages 2225–2234)

      Xinde Tang, Longcheng Gao, Xinghe Fan and Qifeng Zhou

      Article first published online: 17 APR 2007 | DOI: 10.1002/pola.21989

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      Atom transfer radical polymerization was employed to synthesize ABA-type amphiphilic triblock copolymers composed of poly(ethylene glycol) as the hydrophilic blocks (B) and azobenzene-containing polymethacrylate as the hydrophobic blocks (A). The use of difunctional macroinitiators led to triblock copolymers with narrow polydispersities of around 1.20 and controlled number-average molecular weights. These copolymers exhibited unusual liquid-crystalline properties over a wide temperature range and showed photoresponsive isomerization under the irradiation of UV–vis light both in THF solutions and in solid films.

    16. Novel synthesis of biodegradable poly(lactide-co-ethylene glycol) block copolymers (pages 2235–2245)

      Yahia Lemmouchi, Michael C. Perry, Allan J. Amass, Khirud Chakraborty and Francois Schué

      Article first published online: 17 APR 2007 | DOI: 10.1002/pola.21991

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      The polymerization of lactide was carried out with a novel catalyst, potassium hexamethyldisilazide, and with an alcohol as an initiator to yield polymers of controlled molecular weights and narrow polydispersities. The polymerization went to complete conversion at room temperature, with the alcohol appearing as an end group in the polymer. When poly(ethylene glycol) was used as the initiator, block copolymers were obtained, as confirmed by NMR spectroscopy.

    17. Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation (pages 2246–2258)

      V. V. AntiĆ, M. P. AntiĆ, M. N. Govedarica and P. R. DvorniĆ

      Article first published online: 17 APR 2007 | DOI: 10.1002/pola.21992

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      Poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] (PTMDSE), as well as poly(methyldecylsiloxane) (PMDS), were synthesized by Karstedt's catalyst catalyzed hydrosilylation reactions. PTMDSE was obtained by polymerization of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while PMDS was prepared by reaction of 1-decene with poly(methylhydrosiloxe) (PMHS). Kinetics of both reactions was investigated in bulk, with equimolar amounts of the reacting Si[BOND]H and CH[DOUBLE BOND]CH2 groups. The course of the reactions was monitored by quantitative infrared spectroscopy. The formation of PTMDSE followed typical first order kinetics. During the formation of PMDS induction period occurred at temperatures below 44 °C. The kinetics of PTMDSE and PMDS formation was consistent with the proposed reaction mechanisms.

    18. Vinyl copolymers containing pendant 1,3,4-oxadiazole chromophores: Preparation and electrochemical and electroluminescent properties (pages 2259–2272)

      Kun-Ming Yeh and Yun Chen

      Article first published online: 17 APR 2007 | DOI: 10.1002/pola.21990

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      Three soluble vinyl copolymers (P1–P3) containing pendant aromatic 1,3,4-oxadiazole derivatives were prepared. The photoluminescence spectroscopy results revealed that the architecture of P2 and P3 reduced aggregate formation. Both the HOMO and LUMO levels of P1–P3 (−3.09 to −3.81 eV and −5.37 to −5.96 eV) were much lower than those of poly[2-methoxy-5-(2′-ethylhexoxy)-p-phenylenevinylene] (MEH-PPV) (−2.7 eV and −5.02 eV) because of the electron-withdrawing 1,3,4-oxadiazole groups. The performance of an electroluminescence device [indium tin oxide/poly(3,4-ethylene dioxythiophene)/MEH-PPV/Al; maximum luminance = 5860 cd/m2, current efficiency = 1.45 cd/A] was improved significantly to 16,261 cd/m2 and 4.79 cd/A through blending with 50 wt % P2.

    19. Synthesis and characterization of sulfonated poly(benzoxazole ether ketone)s by direct copolymerization as novel polymers for proton-exchange membranes (pages 2273–2286)

      Jinhuan Li and Hongyan Yu

      Article first published online: 17 APR 2007 | DOI: 10.1002/pola.21994

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      A series of novel sulfonated poly(benzoxazole ether ketone)s (SPAEKBO-X) were synthesized by aromatic nucleophilic polycondensation. Benzoxazole-containing sulfonated copolymers were thus more readily obtained in comparison with the conventional poly(phosphoric acid) method. The copolymers were highly soluble in polar and aprotic organic solvents and could form tough and flexible membranes. The membranes' thermal behavior, water uptake, mechanical properties, hydrolytic and oxidative stability, and proton conductivity at 30–90 °C and 95% relative humidity and at 90–130 °C without external humidification were evaluated. The experimental results indicate that SPAEKBO-X copolymers are promising for polymer electrolyte membranes in fuel cells and especially promising for high-temperature fuel-cell applications.

    20. Dendritic polyamine architectures with lipophilic shells as nanocompartments for polar guest molecules: A comparative study of their transport behavior (pages 2287–2303)

      M. Krämer, M. Kopaczynska, S. Krause and R. Haag

      Article first published online: 17 APR 2007 | DOI: 10.1002/pola.21996

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      A simple melt reaction between hyperbranched polyethylenimine with different fatty acids leads to highly efficient dendritic core-shell architectures, which act as nanocompartments for various guest molecules. Parameters, such as the length of the attached alkyl chain, size of the polymer core, concentration of the core-shell architecture in solution, pH and nature of the guest molecule were investigated and compared. Guest molecules that bear anionic groups are readily encapsulated and transferred from the aqueous phase to the organic phase due to multiple anionic-cationic interactions. Also, these dendritic core-shell architectures exhibit enhanced encapsulation properties compared to their linear counterparts.

    21. Butyl acrylate RAFT polymerization in miniemulsion (pages 2304–2315)

      Yingwu Luo, Bei Liu, Zuohe Wang, Jin Gao and Bogeng Li

      Article first published online: 17 APR 2007 | DOI: 10.1002/pola.21999

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      The control over RAFT miniemulsion polymerization of butyl acrylate was found to be highly sensitive to the RAFT structures. Only the RAFT agent with the primary R group and Z group with less stabilizing ability to the intermediate radical is effective to mediate BA miniemulsion polymerization. Molecular weight distribution of the final polymer mediated by RAFT agents with various structures shown here.

    22. New powder coatings with low curing temperature and enhanced mechanical properties obtained from DGEBA epoxy resins and Meldrum acid using erbium triflate as curing agent (pages 2316–2327)

      S. J. García, A. Serra and J. Suay

      Article first published online: 19 APR 2007 | DOI: 10.1002/pola.21998

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      This figure presents a time–temperature diagram for four polymeric systems in order to obtain a 98% of curing conversion, all together with three pictures of the systems applied on steel substrate and tested with an impact resistance test. In this article is proposed a new kind of epoxy systems using Meldrum acid and erbium triflate as the initiator (systems named MA). The new systems offer a high reduction of curing time and temperature with respect to the reference system TBG, which together with very good mechanical properties, makes the new systems very useful binders for organic protective coatings. [A color version of the adjacent figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  3. Rapid Communications

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Notes
    1. You have free access to this content
      Chemical reactions of the conducting polymer poly(3,4-ethylene dioxythiophene) and alcohols (pages 2328–2333)

      John G. D'Angelo, Rene Sawyer, Arvind Kumar, Amber Onorato, Christopher McCluskey, Christopher Delude, Laura Vollenweider, Nicholas Reyes, Rebecca French, Suzanne Warner, Jay Chou, Jason Stenzel, Gregory A. Sotzing and Michael B. Smith

      Article first published online: 19 APR 2007 | DOI: 10.1002/pola.21973

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      We show that a widely used conducting polymer, poly(3,4-ethylene dioxythiophene) (PEDOT), reacts with benzylic alcohols upon heating under an inert atmosphere to give the corresponding homoether and water without the need to attach a secondary reagent or other reactive unit. This reaction does not appear to result from endogenous acid or from a buildup of acid on the polymer. Apart from the water byproduct, small amounts of aldehyde are also produced during this process. Far from being chemically inert, PEDOT facilitates facile reactions with benzylic alcohols. Because alcohols are common additives to conducting polymers, this reaction may be detrimental to the long-term stability of devices using PEDOT.

    2. You have free access to this content
      Original approach to multiblock copolymers via reversible addition–fragmentation chain transfer polymerization (pages 2334–2340)

      Hesna Gemici, Thomas M. Legge, Michael Whittaker, Michael J. Monteiro and Sébastien Perrier

      Article first published online: 19 APR 2007 | DOI: 10.1002/pola.21985

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      α,ω-Thiol-terminated (co)polymers synthesized via reversible addition–fragmentation chain transfer polymerization can be oxidized to yield multiblock copolymers via the formation of disulfide bridges.

  4. Notes

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Notes
    1. You have free access to this content
      Synthesis of arylethyl-functionalized N-alkoxyamine initiators and use in nitroxide-mediated radical polymerization (pages 2341–2349)

      Nicole L. Hill and Rebecca Braslau

      Article first published online: 19 APR 2007 | DOI: 10.1002/pola.21993

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      New functionalized initiators have been synthesized and evaluated for use in nitroxide-mediated radical polymerization. Well-defined polymers have been made of polystyrene and poly(tert-butyl acrylate). These functionalized initiators carry convenient handles for pre- or post-polymerization modification. In particular, primary alcohol, protected carboxylic acid, and amine groups are ideally suited for coupling to peptides or oligosaccharides to prepare polymer–biomolecule hybrids.

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