Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 13

1 July 2011

Volume 49, Issue 13

Pages 2761–2995

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Solubilization of C60 by micellization with a thermoresponsive block copolymer in water: Characterization, singlet oxygen generation, and DNA photocleavage (pages 2761–2770)

      Shin-Ichi Yusa, Shigeki Awa, Masanori Ito, Takeshi Kawase, Tadao Takada, Kenichi Nakashima, Dian Liu, Shigeru Yamago and Yotaro Morishima

      Version of Record online: 29 APR 2011 | DOI: 10.1002/pola.24709

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      Water-soluble diblock copolymer, poly(N-isopropylacrylamide)-block-poly(N-vinyl-2-pyrroridone) (PNIPAMm-b-PNVPn), was found to associate with fullerene (C60), and thus C60 can be solubilized in water. The size of the C60-bound polymer micelle increased with increasing temperature, which was ascribed to the hydrophobic association between dehydrated PNIPAM shells above lower critical solution temperature. The generation of singlet oxygen by photosensitization by the C60-bound polymer micelle was confirmed. Therefore, there may be a hope for a pharmaceutical application of the C60-bound polymer micelle to cancer photodynamic therapy (PDT).

    2. “Clickable” polymers via a combination of RAFT polymerization and isocyanate chemistry (pages 2771–2782)

      John Moraes, Thomas Maschmeyer and Sébastien Perrier

      Version of Record online: 2 MAY 2011 | DOI: 10.1002/pola.24710

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      Two isocyanate-bearing monomers dimethyl meta-isopropenyl benzyl isocyanate (TMI) and 2-isocyanatoethyl methacrylate (ICEMA) were co-polymerized with styrene and methyl methacrylate (MMA), respectively, in a one-pot, two-step method to afford a block co-polymer with an isocyanate-functionalized “anchoring” block and a homopolymer “tail” block. The incorporation of TMI and ICEMA into their respective co-polymers was compared and the resultant block co-polymers were used in a series of coupling reactions. Phenol, polyethylene glycol, and cellulose were used as representative small molecules, polymeric molecules, and solid substrates to study the ability of the isocyanate-bearing moiety to graft onto a variety of substances, thus expounding the versatility of the system.

    3. Zwitterionic shell-crosslinked micelles from block-comb copolymer of PtBA-b-P(PEGMEMA-co-DMAEMA) (pages 2783–2789)

      Zong-Lei Ding, Wei-Dong He, Jing Tao, Wen-Xing Jiang, Li-Ying Li and Ting-Ting Pan

      Version of Record online: 28 APR 2011 | DOI: 10.1002/pola.24711

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      Well-defined block-comb copolymer of PtBA-b-P(PEGMEMA-co-DMAEMA) was synthesized through RAFT polymerizations. After the self-assembly into micelles followed by shell crosslinking and core hydrolysis, zwitterionic SCK micelles of PAA-b-P(PEGMEMA-co-DMAEMA) were obtained. The zwitterionic SCK micelles did not show iep behavior even though PAA units were more than PDMEMA units. However, the presence of PAA negative charge still has its influence. The absence of isoelctric point for zwitterionic SCK micelles can be contributed to PEG short chains around PDMAEMA shell.

    4. Main-chain chiral poly(2-oxazoline)s: Influence of alkyl side-chain on secondary structure formation in solution (pages 2790–2801)

      Meta M. Bloksma, Sarah Rogers, Ulrich S. Schubert and Richard Hoogenboom

      Version of Record online: 28 APR 2011 | DOI: 10.1002/pola.24712

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      By varying the side-chain length on the second position of chiral main-chain poly(2-oxazoline)s, the solubility of the polymer changes resulting in differences in the persistence length of the secondary structure formed in solution. With relatively long side-chains, the structure can alter from a fully stretched polymer into a more compact structure depending on the polarity of the solvent. The most significant change in structure formation occurs when the alkyl side-chain length is increased from octyl groups to nonyl groups.

    5. Synthesis of amphiphilic ABC triblock copolymers by single electron transfer nitroxide radical coupling reaction in tetrahydrofuran (pages 2802–2810)

      Wencheng Lin, Rongkuan Jing, Guowei Wang and Junlian Huang

      Version of Record online: 28 APR 2011 | DOI: 10.1002/pola.24713

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      A series of amphiphilic ABC triblock copolymers were prepared by combination of single electron transfer nitroxide radical coupling (SETNRC) reaction, anionic technique, and atom transfer radical polymerization. The SETNRC reaction was carried out in a weakly polar solvent, tetrahydrofuran. The effect of reaction time and polymer chain length on the efficiency was investigated. The rate of reaction was rapid in the first 5 min, and almost finished in 2 h, and the efficiency is as high as 91.6%.

    6. Synthesis of H-shaped A3BA3 copolymer by methyl-2-nitrosopropane induced single electron transfer nitroxide radical coupling (pages 2811–2817)

      Zhongning Zhang, Guowei Wang and Junlian Huang

      Version of Record online: 28 APR 2011 | DOI: 10.1002/pola.24714

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      Using a radical trapping agent MNP as precursor of nitroxide radical, a novel amphiphilic H-shaped PEO3-PS-PEO3 copolymer was obtained by SETNRC with high efficiency of 90% within 60 min using a single precursors of PEO3-(PS-Br) in one-pot.

    7. SET–LRP of N-isopropylacrylamide in the presence of chain transfer agent (pages 2818–2822)

      Eylem Turan and Tuncer Caykara

      Version of Record online: 2 MAY 2011 | DOI: 10.1002/pola.24715

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      The single-electron transfer living radical polymerization (SET–LRP) in the presence of chain transfer agent (CTA) was first extended to N-isopropylacrylamide (NIPAM) to synthesis poly(N-isopropylacrylamide) with a low molecular weight and a low polydispersity index. This was achieved by using Cu(I)/2,2′-bipyridine (2,2′-bpy) as the catalyst, 2-bromopropionyl bromide (2-BPB) as the initiator, 2-mercaptoethylamine as the chain transfer agent, and N,N-dimethylformamide (DMF) as the solvent.

    8. Polyamide 6-polycaprolactone multiblock copolymers: Synthesis, characterization, and degradation (pages 2823–2833)

      Seda Cakir, René Kierkels and Cor Koning

      Version of Record online: 2 MAY 2011 | DOI: 10.1002/pola.24716

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      Low molar mass polycaprolactone was successfully incorporated into polyamide 6 by solution and solid state polymerization after synthesis of both components with desired end groups. The structure and thermal properties of polymers before and after incorporation were analyzed by SEC, FTIR, NMR, titration analysis as well as TGA and DSC. DSC data, together with an increase in molar mass pointed to a multiblock structure with almost maintained melting temperatures. Degradation of polymers were perfomed via enzymatic and hydrolytic routes at 25 °C and followed by weight loss analysis, SEM and SEC.

    9. Alternating copolymerization of bis(hexafluoroisopropyl) fumarate with styrene and vinyl pentafluorobenzoate: Transparent and low refractive index polymers (pages 2834–2838)

      Hongxiang Teng, Weihong Liu, Yasuhiro Koike and Yoshiyuki Okamoto

      Version of Record online: 4 MAY 2011 | DOI: 10.1002/pola.24717

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      Bis(hexafluoroisopropyl) fumarate (BHFIPF), which did not homopolymerize with free radical initiators, can copolymerize with styrene and vinyl pentafluorobenzoate (VPFB) to produce the alternating copolymers. The glass transition temperatures (Tg) and the thermal degradation temperatures (Td) of the BHFIPF-styrene and BHFIPF-VPFB copolymers were characterized, respectively. The films obtained by casting from THF solutions of these copolymers were flexible and transparent. Their refractive indices were quite low due to the large amount of fluorine.

    10. Sequential functionalization of janus-type dendrimer-like poly(ethylene oxide)s with camptothecin and folic acid (pages 2839–2849)

      Xiaoshuang Feng, Julien Pinaud, Elliot L. Chaikof, Daniel Taton and Yves Gnanou

      Version of Record online: 4 MAY 2011 | DOI: 10.1002/pola.24718

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      Janus-type dendrimer-like poly(ethylene oxide)s of 1st, 2nd, and 3rd generation carrying terminal hydroxyl functions on one side and cleavable ketal groups on the other were used as substrates to conjugate folic acid as a folate receptors and camptothecin (CPT) as a therapeutic drug in an sequential fashion by “click chemistry.”

    11. Various brush polymers through ring opening metathesis polymerization and nitroxide radical coupling reaction (pages 2850–2858)

      Nese Cerit, Nese Cakir, Aydan Dag, Okan Sirkecioglu, Hakan Durmaz, Gurkan Hizal and Umit Tunca

      Version of Record online: 28 APR 2011 | DOI: 10.1002/pola.24719

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      Numerous brush copolymers and terpolymers were prepared via a combination of ring-opening metathesis polymerization (ROMP) and nitroxide radical coupling (NRC) click reaction. A TEMPO-terminated poly(ethylene glycol) (PEG) or -poly(ε-caprolactone) (PCL) (PEG11-TEMPO or PCL23-TEMPO) is grafted as a side chain onto a ROMP-generated PONB main backbone with bromide pendant groups (PONB20-Br) using the NRC click reaction to yield related brush copolymers, PONB20-g-PEG11 or PONB20-g-PCL23 catalyzed by Cu(I), Cu(0), and N,N,N,N,N″-pentamethyldiethylenetriamine in N,N-dimethylformamide at room temperature. Additionally, a ROMP-generated brush copolymer PONB9-g-poly(methyl methacrylate)24 (PMMA)24-Cl was reacted with a PEG11-TEMPO or a PCL23-TEMPO precursor via the NRC click reaction to yield a corresponding brush terpolymer, PONB9-g-(PMMA24-b-PEG11) or PONB9-g-(PMMA24-b-PCL23) under a similar reaction condition described above.

    12. Synthesis of poly(ethylene glycol)/polypeptide/poly(D,L-lactide) copolymers and their nanoparticles (pages 2859–2865)

      Hyunpyo Lee, Jun Beum Park and Ji Young Chang

      Version of Record online: 10 MAY 2011 | DOI: 10.1002/pola.24720

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      Core-shell structured nanoparticles of poly(ethylene glycol) (PEG)/polypeptide/poly(D,L-lactide) copolymers were prepared and their structures and properties were investigated. The polypeptide blocks resided at the interface between a hydrophilic PEG shell and a hydrophobic PLA core in the nanoparticles and enhanced the stability of the nanoparticles via intermolecular hydrogen bonding.

    13. Synthesis and characterization of pH-sensitive and thermosensitive double hydrophilic graft copolymers (pages 2866–2877)

      You-Liang Tu, Cheng-Chien Wang and Chuh-Yung Chen

      Version of Record online: 2 MAY 2011 | DOI: 10.1002/pola.24721

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      We have prepared a series of polyNIPAM-co-poly(L-lysine) graft copolymers, which have coil-to-helix transitions from pH 6 to pH 12 and form uniform nano-scale micelle structures at pH 12. The graft copolymers also could form micelles at 50 °C in pH 6 buffer solution due to slightly polymer aggregation. With temperature and pH increased, both the deprotonated PLLys side chains and PNIPAm backbone become hydrophobic, leading to polymer precipitation.

    14. Highly active, thermo-responsive polymeric catalytic system for reuse in aqueous and organic CuAAC reactions (pages 2878–2885)

      Sofie Wallyn, Mieke Lammens, Rachel K. O'reilly and Filip Du Prez

      Version of Record online: 4 MAY 2011 | DOI: 10.1002/pola.24723

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      Highly active and reusable polymeric catalysts were produced by RAFT polymerization of N-isopropyl acrylamide with a TBTA-containing monomer, followed by copper(I) loading. The copper-loaded thermo-responsive copolymers are excellent, recyclable catalysts for CuAAC reactions in both water and organic solvent. The polymer catalyst system was regenerated via extraction by making use of its LCST-behavior.

    15. The influence of electron deficient unit and interdigitated packing shape of new polythiophene derivatives on organic thin-film transistors and photovoltaic cells (pages 2886–2898)

      Hoyoul Kong, Shinuk Cho, Dong Hoon Lee, Nam Sung Cho, Moo-Jin Park, In Hwan Jung, Jong-Hwa Park, Chan Eon Park and Hong-Ku Shim

      Version of Record online: 2 MAY 2011 | DOI: 10.1002/pola.24724

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      A series of new polythiophene derivatives containing a thiazole ring as an electron deficient unit were synthesized and characterized. A copolymer in an H-shaped packing system, PTTz, exhibited the highest TFT mobility (μ = 0.050 cm2 V−1 s−1) with a high on/off ratio of 106 and a solar cell performance (PCE = 1.39%, Jsc = 6.58 mA cm−2, and Voc = 0.58 V).

    16. Efficient carbonyl hydrosilylation reaction: Toward EVA copolymer crosslinking (pages 2899–2907)

      Julien Bonnet, Veronique Bounor-Legaré, Fernande Boisson, Flavien Mélis and Philippe Cassagnau

      Version of Record online: 2 MAY 2011 | DOI: 10.1002/pola.24725

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      The hydrosilylation reaction of carbonyl groups of octyl acetate and 4-heptyl acetate and SiH groups of hydride-terminated polydimethylsiloxane at high temperature (100–130 °C) was catalyzed by triruthenium dodecacarbonyl Ru3(CO)12. This reaction was extended to the crosslinking of EVA copolymer in the same range of temperature. The formation of EVA chemical network was demonstrated by NMR spectroscopy and by measuring the gel fraction of EVA chains in hot toluene.

    17. Poly(arylene ether)s with pendant diphenyl phosphoryl groups: Synthesis, characterization, and thermal properties (pages 2908–2915)

      Kevin Tienda, Zhenning Yu, Fadwa Constandinidis, Andria Fortney, William A. Feld and Eric Fossum

      Version of Record online: 2 MAY 2011 | DOI: 10.1002/pola.24726

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      The synthesis of poly(arylene ether)s, PAEs, containing pendant diphenylphosphoryl groups has been achieved via the meta activated nucleophilic aromatic substitution reaction of 3,5-difluorotriphenylphosphine oxide with a variety of bisphenols as nucleophilic reaction partners. The resulting PAEs possessed relatively high molecular weights, were completely amorphous and readily soluble in many organic solvents. 103:

    18. Synthesis of polyacrylonitrile by single-electron transfer-living radical polymerization using Fe(0) as catalyst and its adsorption properties after modification (pages 2916–2923)

      Delong Liu, Hou Chen, Ping Yin, Naiyi Ji, Guangxi Zong and Rongjun Qu

      Version of Record online: 4 MAY 2011 | DOI: 10.1002/pola.24727

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      Well-defined polyacrylonitrile (PAN) was synthesized by single-electron transfer-living radical polymerization using Fe(0) as a novel catalyst, carbon tetrachloride as initiator, hexamethylenetetramine as N-ligand, and N,N-dimethylformamide as the solvent. First-order kinetic studies and chain extension of methyl methacrylate with PAN as macroinitiator indicated that this polymerization proceeded in a “living”/controlled manner. Prepared PAN (Mn = 19,740, PDI = 1.15) was modified with NH2OH·HCl and used for the adsorption of Hg2+ from aqueous solutions. The maximal saturated extent of adsorption of Hg2+ was 4.8 mmol g−1.

    19. Samarium powder as catalyst for SET-LRP of acrylonitrile in 1,1,1,3,3,3-hexafluoro-2-propanol for control of molecular weight and tacticity (pages 2924–2930)

      Hou Chen, Guangxi Zong, Lingfang Chen, Min Zhang, Chunhua Wang and Rongjun Qu

      Version of Record online: 10 MAY 2011 | DOI: 10.1002/pola.24728

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      Samarium powder was applied as a catalyst for single electron transfer-living radical polymerization (SET-LRP) of acrylonitrile (AN) in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) with 2-Bromopropionitrile as initiator and N,N,N′,N′-tetramethylethylenediamine as ligand. First-order kinetics of polymerization with respect to the monomer concentration, linear increase of the molecular weight with monomer conversion, and the highly syndiotactic polyacrylonitrile (PAN) obtained indicate that SET-LRP of AN could simultaneously control molecular weight and tacticity of PAN. An increase in syndiotacticity of PAN obtained in HFIP was observed compared with that obtained by SET-LRP in N,-N-dimethylformamide (DMF). The syndiotacticity of PAN prepared by SET-LRP of AN using Sm powder as catalyst in DMF was higher than that prepared with Cu powder as catalyst. The block copolymer PAN-b-polymethyl methacrylate (52,310 molecular weight and 1.34 polydispersity) was successfully prepared.

    20. Synthesis of nonsymmetric chain end functionalized polyisobutylenes (pages 2931–2940)

      Olubummo Adekunle, Florian Herbst, Katharina Hackethal and Wolfgang H. Binder

      Version of Record online: 12 MAY 2011 | DOI: 10.1002/pola.24729

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      For the first time the synthesis of nonsymmetric α-ω-functionalized poly(isobutylenes) bearing different supramolecular moieties on their chain ends is achieved. A combination of methyl-styrene epoxide as initiator for the cationic living polymerization, followed by quenching reaction with 3-bromopropyloxy-benzene (BPB) and subsequent azide/alkyne-“click”-chemistry of the α-endgroup and ω-endgroup leads to the finally nonsymmetrical α-ω-functionalized poly(isobutylenes). Extensive 1H-NMR and matrix-assisted laser desorption/ionization MALDI-mass spectroscopy prove the quantitative transformations of the endgroups of the polymers, which are important binding-sites for nanoparticles and subsequent supramolecular ordering.

    21. Biodegradable thermo- and pH-responsive hydrogels for oral drug delivery (pages 2941–2951)

      Zhe Zhang, Li Chen, Mingxiao Deng, Yunyan Bai, Xuesi Chen and Xiabin Jing

      Version of Record online: 10 MAY 2011 | DOI: 10.1002/pola.24730

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      A series of pH- and temperature-sensitive hydrogels were designed and synthesized by the radical crosslinking between hydroxypropylcellulose-g-acrylic acid and poly(L-glutamic acid-g-2-hydroxylethyl methacrylate) (PGH) using ammonium persulfate as the initiator. The in vitro release of bovine serum albumin from the hydrogels demonstrated that the drug release rate in artificial gastric juice was slower than that in artificial intestinal liquid due to the protonation of the PGH part at an acidic condition. The results show the possibility of using this pH- and temperature-sensitive hydrogel as an intelligent drug delivery carrier.

    22. Functionalization of parylene during its chemical vapor deposition (pages 2952–2958)

      Maria Naddaka, Florian Asen, Sylwia Freza, Maciej Bobrowski, Piotr Skurski, Edith Laux, Jerome Charmet, Herbert Keppner, Monika Bauer and Jean-Paul Lellouche

      Version of Record online: 10 MAY 2011 | DOI: 10.1002/pola.24731

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      The potential and mechanism of the functionalization of Parylene [poly(paraxylylene)] with acrylate-based molecules during its chemical vapor deposition were predicted using theoretical calculations and proved experimentally. A direct correlation was found between predicted and experimental reactivities. In a second step, we evaluated the reactivity of such electrophilic acrylate-modified Parylene films via their simple modification by various amine-containing species.

    23. Metal-free synthesis of novel biobased dihydroxyl-terminated aliphatic polyesters as building blocks for thermoplastic polyurethanes (pages 2959–2968)

      Donglin Tang, Bart A. J. Noordover, Rafael J. Sablong and Cor E. Koning

      Version of Record online: 11 MAY 2011 | DOI: 10.1002/pola.24732

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      The organic base 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) which was developed as the catalyst for the ring-opening polymerization of cyclic esters, is used here for catalyzing the polycondensation of renewable dimethylesters with renewable diols to prepare well defined, telechelic hydroxyl-terminated aliphatic polyesters. It is shown that TBD is more effective than the conventional catalyst titanium butoxide for this type of polycondensation. One of the polyesters, poly(1,2-dimethylethylene adipate) (PDMEA) was synthesized for the first time and it is certified to be fully amorphous. The PDMEA-based thermoplastic polyurethaneureas (TPUUs) were prepared and their mechanical properties indicate that they are suitable for cardiovascular medical applications.

    24. Alternating narrow band gap copolymers derived from indeno[1,2-b]fluorene and thiophene-cored-thieno[3,4-b]pyrazine derivatives—Synthesis, characterization and comparative studies of photochemical stability (pages 2969–2979)

      Yangjun Xia, Junfeng Tong, Bin Li, Chenglong Wang and Hongzhong Liu

      Version of Record online: 12 MAY 2011 | DOI: 10.1002/pola.24735

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      Three alternating NBG-conjugated polymers derived from IF and DTTP, DPTP, and DOTP, named as PIF-DTTP, PIF-DPTP, and PIF-DOTP, respectively, and were synthesized and characterized. Comparative studies of photochemical stabilities of the PIF-DTTP, PIF-DPTP, and copolymer derived from IF and 5,7-dithien-2-yl-thieno[3,4-b]pyrazine (named as PIF-DTP) were investigated by UV absorption, PL spectra and FT-IR etc of the polymers as a function of UV irradiation time. The studies indicated that the photochemical stability of thieno[3,4-b]pyrazine (TP) ring can be increased by the introducing phenyl group on the TP, which could be used as a durable electron deficient moiety for NBG organic semiconductors.

    25. Ab initio RAFT emulsion polymerization of butadiene using the amphiphilic poly(acrylic acid-b-styrene) trithiocarbonate as both surfactant and mediator (pages 2980–2989)

      Renzhong Wei, Yingwu Luo and Pinghong Xu

      Version of Record online: 12 MAY 2011 | DOI: 10.1002/pola.24736

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      The amphiphilic poly(acrylic acid-b-styrene) trithiocarbonate was used as both surfactant and mediator in the ab initio emulsion polymerization of butadiene. The neutralization on acrylic acid units played significant influence on the gelation. In non-neutralized conditions, the gelation was much retarded so that the highest accessible molecular weight was much increased to 23 kg mol−1.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Novel macrothiols for the synthesis of a structurally comprehensive dendritic library using thiol–ene click chemistry (pages 2990–2995)

      Marie V. Walter, Pontus Lundberg, Anders Hult and Michael Malkoch

      Version of Record online: 13 MAY 2011 | DOI: 10.1002/pola.24742

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      Monodisperse high-molecular weight macrothiols were synthesized and efficiently coupled to various allylic precursors via thiol–ene click chemistry. A comprehensive dendritic library was obtained in good yields and short reaction times including conventional dendrimers as well as more sophisticated structures such as dendritic-linear hybrids or asymmetrical dendrimers. Finally, the versatility of this approach allowed the construction of advanced materials in both aqueous and organic solvents.