Precise synthesis and surface structures of architectural per- and semifluorinated polymers with well-defined structures

Giannetti, 2001, Featured article. Semi-crystalline fluorinated polymers, Polym Int, 50, 10, 10.1002/1097-0126(200101)50:1<10::AID-PI614>3.0.CO;2-W Hillmyer, 2002, Synthesis and self-assembly of fluorinated block copolymers, J Polym Sci, 40, 1, 10.1002/pola.10074 Reisinger, 2002, Synthesis of fluorinated polymers by chemical modification, Prog Polym Sci, 27, 971, 10.1016/S0079-6700(02)00004-7 Imae, 2003, Fluorinated polymers, Curr Opin Colloid Interface Sci, 8, 307, 10.1016/S1359-0294(03)00050-5 Krishnan, 2004, Fluorinated polymers: liquid crystalline properties and applications in lithography, Chem Rec, 4, 315, 10.1002/tcr.20022 Hansen, 2007, Fluoropolymer materials and architectures prepared by controlled radical polymerizations, Eur Polym J, 43, 255, 10.1016/j.eurpolymj.2006.11.016 Xia, 1999, Atom transfer radical polymerization in supercritical carbon dioxide, Macromolecules, 32, 4802, 10.1021/ma9900380 Lüning, 2001, Correlation of surface and bulk order in low surface energy polymers, Macromolecules, 34, 1128, 10.1021/ma0001584 Jankova, 2003, Preparation of poly(2,3,4,5,6-pentafluorostyrene) and block copolymers with styrene by ATRP, Macromolecules, 36, 1753, 10.1021/ma021039m Borkar, 2004, New highly fluorinated styrene-based materials with low surface energy prepared by ATRP, Macromolecules, 37, 788, 10.1021/ma034952b Yong, 1997, Synthesis of fluorinated block copolymers and their application as novel polymerization surfactants in supercritical carbon dioxide, Chem Commun, 1811, 10.1039/a705399a Ishizone, 1999, Anionic polymerizations of perfluoroalkyl methacrylates and synthesis of well-defined ABC triblock copolymers of methacrylates containing hydrophilic, hydrophobic, and perfluoroalkyl groups, Polym J, 31, 983, 10.1295/polymj.31.983 Choi, 1988, Living cationic homo- and copolymerization of vinyl ethers bearing a perfluoroalkyl pendant, Polym J, 20, 201, 10.1295/polymj.20.201 Percec, 1992, JMS—Pure Appl Chem A, 29, 723 Vandooren, 1994, Living cationic polymerization of 1H, 1H, 2H, 2H perfluorooctyl vinyl ether, Polym Bull, 32, 387, 10.1007/BF00587879 Hunt, 1993, End-functionalized polymers. 1. Synthesis and characterization of perfluoroalkyl-terminated polymers via chorosilane derivatives, Macromolecules, 26, 4854, 10.1021/ma00070a020 Affrossman, 1994, Surface segregation in blends of hydrogenous polystyrene and perfluorohexane end-capped deuterated polystyrene, studied by SSIMS and XPS, Macromolecules, 27, 1588, 10.1021/ma00084a047 Elman, 1994, A neutron reflectivity investigation of surface and interface segregation of polymer functional end groups, Macromolecules, 27, 5341, 10.1021/ma00097a013 Schaub, 1996, Surface modification via chain end segregation in polymer blends, Macromolecules, 29, 3982, 10.1021/ma9510810 Affrossman, 1996, Surface segregation in blends of polystyrene and perfluorohexane double end capped polystyrene studied by static SIMS, ISS, and XPS, Macromolecules, 29, 5432, 10.1021/ma950900d Hopkinson, 1997, Equilibrium concentration profiles of physically end tethered polystyrene molecules at the air–polymer interface, Polymer, 38, 87, 10.1016/S0032-3861(96)00482-X Yuan, 1999, Effects of low-energy end groups on the dewetting dynamics of poly(styrene) films on poly(methyl methacrylate) substrates, Macromolecules, 32, 2329, 10.1021/ma980774o Jiang, 2001, Effect of chain end group on surface glass transition temperature of thin polymer film, Phys Lett A, 281, 363, 10.1016/S0375-9601(01)00150-5 Hadjichristidis, 1999, Asymmetric star polymer synthesis:synthesis and properties, Adv Polym Sci, 42, 71, 10.1007/3-540-68310-0_2 Sugiyama, 1996, Synthesis of end-functionalized polymer by means of living anionic polymerization, 7: reaction of anionic living polymers with perfluoroalkyl halides, Macromol Chem Phys, 197, 3149, 10.1002/macp.1996.021971008 1996, 261 Hirao, 2003, Synthesis of chain-end-functionalized poly(methyl methacrylate)s with a definite number of benzyl bromide moieties and their application to star-branched polymers, Macromolecules, 36, 9742, 10.1021/ma035264v El-Shehawy, 2005, Precise synthesis of novel chain-end-functionalized polystyrenes with a definete number of perfluorooctyl groups and their surface characterization, Macromolecules, 38, 8285, 10.1021/ma050457z McLain, 1996, Surface properties and methathesis synthesis of block copolymers including perfluoroalkyl-ended polyethylenes, Macromolecules, 29, 8211, 10.1021/ma960593r Koh, 2005, Precision synthesis of a fluorinated polyhedral oligomeric silsesquioxane-terminated polymer and surface characterization of its blend film with poly(methylmethacrylate), Macromolecules, 38, 1264, 10.1021/ma047636l Destarac, 2000, Atom transfer radical polymerization initiated with vinylidene fluoride telomers, Macromolecules, 33, 4613, 10.1021/ma9918351 Shi, 2004, Synthesis of block copolymers possessing fluoropolymer and non-fluoropolymer segments by radical polymerization, Macromolecules, 37, 2084, 10.1021/ma030035u Perrier, 2003, Preparation of fluorinated copolymers by cupper-mediated living radical polymerization, Macromolecules, 36, 9042, 10.1021/ma0259822 Feiring, 2000, Fluorocarbon-ended polymers: metal catalyzed radical and living radical polymerizations initiated by perfluoroalkylsulfonyl halides, J Polym Sci Part A: Polym Chem, 38, 3313, 10.1002/1099-0518(20000915)38:18<3313::AID-POLA100>3.0.CO;2-D Perrier, 2002, Preparation of fluorinated methacrylic copolymer by cupper mediated living radical polymerization, Tetrahedron, 58, 4053, 10.1016/S0040-4020(02)00274-0 Li, 2006, Novel, well-defined polystyrene with a fluorine cluster end-capped group: synthesis, characterization, and surface properties, J Polym Sci Part A: Polym Chem, 44, 3853, 10.1002/pola.21486 O’Rourke Muisener, 2003, Measurement and modeling of end group concentration depth profles for w-fluorosilene polystyrene and its blends, Macromolecules, 36, 2956, 10.1021/ma021623v Mason, 2001, Surface energy and surface composition of end-fluorinated polystyrene, Adv Colloid Interface Sci, 94, 1, 10.1016/S0001-8686(01)00051-3 Jiang, 2001, Surface relaxation behavior of proton- and perfluoroalkyl-terminated poly(2-vinylpyridine)films, Polymer, 42, 8959, 10.1016/S0032-3861(01)00384-6 Huang, 1998, Using surface active random copolymers to control the domain orientation in diblock copolymer thin film, Macromolecules, 31, 7641, 10.1021/ma980705+ Glass JE. editors. Polymers in aqueous media, performance through association. ACS symposium series 223. Washington, DC: American Chemical Society; 1989. Schulz DN, Glass JE. editors. Polymers as rheology modifiers. ACS symposium series 462. Washington, DC: American Chemical Society; 1991. Glass JE. editor. Hydrophilic polymers: performance with environmental acceptance. ACS Advance in chemistry series 248. Washington, DC: American Chemical Society; 1996. Xu, 1997, Synthesis, characterization, and rheological behavior of polyethylene glycols end-capped with fluorocarbon hydrophobe, Langmuir, 13, 2447, 10.1021/la960799l Zhang, 1998, Synthesis and characterization of one-ended perfluorocarbon-functionalized derivatives of poly(ethylene glycol)s, Macromolecules, 31, 2815, 10.1021/ma9712256 Tae, 2001, Hydrogels with controlled, surface erosion characteristics from self-assembly of fluoroalkyl-ended poly(ethylene glycol), Macromolecules, 34, 6409, 10.1021/ma0107511 Su, 1997, Adsorption of end-functionalized poly(ethylene oxide)s to the poly(ethylene oxide)–air interface, Macromolecules, 32, 840, 10.1021/ma961396v Su, 1998, Surface activity of perfluorodecanoyl end-capped poly(ethylene oxide) and associated adsorption behavior to the air–water interface, Polymer, 39, 4655, 10.1016/S0032-3861(97)10318-4 Jannasch, 1998, Surface structure and dynamics of block and graft copolymers having fluorinated poly(ethylene oxide) chain ends, Macromolecules, 31, 1341, 10.1021/ma971351+ Calvet, 2003, Perfluoroalkyl end-caped poly(ethylene oxide). Synthesis, characterization, and rheological behavior in aqueous solution, Macromolecules, 36, 449, 10.1021/ma011729a Hoang K, 2004, Aqueous solubilization of highly fluorinated molecules by semifluorinated surfactants, Langmuir, 20, 7347, 10.1021/la049128a Ren, 1995, Spectroscopic characterization of polymer adsorption at the air–solution interface, Macromolecules, 28, 358, 10.1021/ma00105a050 Weberskirch, 2000, Design and synthesis of a two compartment micellar system based on the self-association behavior of poly(N-acylethyleneimine) end-capped with a fluorocarbon and a hydrocarbon chain, Macromol Chem Phys, 201, 995, 10.1002/1521-3935(20000601)201:10<995::AID-MACP995>3.0.CO;2-T Zhang, 1999, Synthesis of fluorine-containing block copolymers via ATRP 2. Synthesis and characterization of semifluorinated di- and triblock copolymers, Polymer, 40, 5439, 10.1016/S0032-3861(99)00029-4 Lim, 2002, Synthesis and properties of semifluorinated block copolymers containing poly(ethylene oxide) and poly(fluorooctyl methacrylate) via atom transfer radical polymerization, Polymer, 43, 7043, 10.1016/S0032-3861(02)00636-5 Hussain, 2002, Synthesis and characterization of poly(ethylene oxide) and poly(perfluorohexylethyl methacrylate) containing triblock copolymers, Macromol Chem Phys, 203, 2103, 10.1002/1521-3935(200210)203:14<2103::AID-MACP2103>3.0.CO;2-X Li, 2002, Preparation and surface properties of fluorine-containing diblock copolymers, Polymer, 43, 4079, 10.1016/S0032-3861(02)00202-1 Andruzzi, 2002, Engineering low surface energy polymers through molecular design: synthetic routes to fluorinated polystyrene-based block copolymers, J Mater Chem, 12, 1684, 10.1039/b200891b Gopalan, 2002, Fluorinated mesogen-jacketed liquid-crystalline polymers as surface-modifing agents: design, synthesis, and characterization, Macromol Chem Phys, 203, 1573, 10.1002/1521-3935(200207)203:10/11<1573::AID-MACP1573>3.0.CO;2-Z Radhakrishnan, 2004, Synthesis of semifluorinated block copolymers by atom transfer radical polymerization, J Polym Sci Part A Polym Chem, 42, 853, 10.1002/pola.11023 Hikita, 2004, Aggregation states and surface wettability in films of poly(styrene-block-perfluorooctyl ethyl acrylate) diblock copolymers synthesized by atom transfer radical polymerization, Langmuir, 20, 5304, 10.1021/la049556g Shemper, 2004, Synthesis and characterization of statistical and block fluorinated copolymers with linear and star-like architectures via ATRP, Eup Polym J, 40, 651, 10.1016/j.eurpolymj.2003.12.010 Jankova, 2005, Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization, J Fluorine Chem, 126, 241, 10.1016/j.jfluchem.2004.11.002 Galli, 2005, Low surface energy characteristics of mesophase-forming ABC and ACB triblock copolymers with fluorinated B blocks, Mol Cryst Liq Cryst, 441, 211, 10.1080/154214091009770 Guan, 1994, Fluorocarbon-based heterophase polymeric materials. 1. Block copolymer surfactants for carbon dioxide applications, Macromolecules, 27, 5527, 10.1021/ma00098a002 Kassis, 1996, XPS studies of fluorinated acrylate polymers and block copolymers with polystyrene, Macromolecules, 29, 3247, 10.1021/ma951782x Arnold, 2002, Microphase separated block copolymers comprising low surface energy fluorinated blocks and hydrophilic blocks: synthesis and characterization, Macromolecules, 35, 3697, 10.1021/ma0119631 Kim, 1999, Synthesis of block copolymers having perfluoroalkyl and silicone-containing side chains using diazo macroinitiator and their surface properties, J Appl Polym Sci, 74, 1917, 10.1002/(SICI)1097-4628(19991121)74:8<1917::AID-APP5>3.0.CO;2-G Bertolucci, 2004, Wetting behavior of films of new fluorinated styrene-siloxane block copolymers, Macromolecules, 37, 3666, 10.1021/ma035934x Hirao A, Sugiyama K. Unpublished results. Li, 2004, Facile fabrication of nanocellular block copolymer thin films using supercritical carbon dioxide, Adv Mater, 16, 1226, 10.1002/adma.200400264 Yokoyama, 2005, Nanocellular structures in block copolymers with CO2-philic blocks using CO2 as a blowing agent: crossover from micro- to nanocellular structures with depressurization temperature, Macromolecules, 38, 10516, 10.1021/ma051757j Li, 2006, CO2 foaming in thin film of block copolymer containing fluorinated blocks, Macromolecules, 39, 4746, 10.1021/ma060325l Tanaka, 1999, A study of three-phase structures in ABC triblock copolymers, Polym J, 31, 989, 10.1295/polymj.31.989 Busse, 2002, Synthesis of amphiphilic block copolymers based on tert-butyl methacrylate and 2-(N-methylperfluorobutanesulfonamide)ethyl methacrylate and its behavior in water, Macromolecules, 35, 178, 10.1021/ma0116809 Krupers, 1997, Synthesis and characterization of semifluorinated polymers via group transfer polymerization, J Fluorine Chem, 82, 119, 10.1016/S0022-1139(96)03569-5 Krupers, 1997, Semifluorinated diblock copolymers. Synthesis, characterization, and amphiphilic properties, Macromol Chem Phys, 198, 2163, 10.1002/macp.1997.021980714 Yang, 2000, Low-surface-energy fluoromethacrylate block copolymers with patternable elements, Chem Mater, 12, 33, 10.1021/cm990241+ Matsumoto, 1999, Water-soluble fluorine-containing amphiphilic block copolymer: synthesis and aggregation behavior in aqueous solution, Macromolecules, 32, 7122, 10.1021/ma990800y Matsumoto, 2000, Perfluoroalkyl-philic character of poly(2-hydroxyethyl vinyl ether)-block-poly[2-(2,2,2-trifluoroethoxy)ethyl vinyl ether] micelles in water: selective solubilization of perfluorinated compounds, Macromolecules, 33, 8295, 10.1021/ma001153+ Zhu, 2005, Synthesis and self-assembly of highly incompatible polybutadiene-poly(hexafluoropropylene oxide) diblock copolymers, J Polym Sci: Part B: Polym Phys, 43, 3685, 10.1002/polb.20621 Böker, 2002, Selective alteration of polymer surfaces by thermal cleavage of fluorinated side chains, Macromolecules, 35, 4929, 10.1021/ma011938v Brantley, 2004, Fluorinated polymer films from acylation of ATRP surface-initiated poly(hydroxyethyl methacrylate), Macromolecules, 37, 1476, 10.1021/ma035471v Iyengar, 1996, Surface segregation studies of fluorine-containing diblock copolymers, Macromolecules, 29, 1229, 10.1021/ma950544z Wang, 1997, Liquid crystalline, semifluorinated side group block copolymers with stable low energy surfaces: synthesis, liquid crystalline structure, and critical surface tension, Macromolecules, 30, 1906, 10.1021/ma961412o Genzer, 2000, The orientation of semifluorinated alkanes attached to polymers at the surface of polymer films, Macromolecules, 33, 1882, 10.1021/ma991182o Genzer, 2000, Temperature dependence of molecular orientation on the surfaces of semifluorinated polymer thin films, Langmuir, 16, 1993, 10.1021/la9910327 Hayakawa, 2000, Effect of changing molecular end groups on surface properties: synthesis and characterization of poly(styrene-b-semifluorinated isoprene) block copolymers with –CF2H end groups, Macromolecules, 33, 8012, 10.1021/ma992112k Li, 2002, Semifluorinated aromatic side-group polystyrene-based block copolymers: bulk structure and surface orientation studies, Macromolecules, 35, 8078, 10.1021/ma020463k You, 2006, Controlled and suppression of surface relief grating in liquid-crystalline perfluoroalkyl-azobenzene polymers, Adv Funct Mater, 16, 1577, 10.1002/adfm.200500711 Genzer, 2000, Molecular orientation of single and two armed monodendron semifluorinated chains on “soft” and “hard” surfaces studied using NEXAFS, Macromolecules, 33, 6068, 10.1021/ma991710w Xiang, 2000, Surface stability in liquid-crystalline block copolymers with semifluorinated monodendron side groups, Macromolecules, 33, 6106, 10.1021/ma992111s Hexemer, 2004, Managing polymer surface structure using surface active block copolymer mixtures, J Polym Sci Part B: Polym Phys, 42, 411, 10.1002/polb.10686 Hwang, 1995, Block copolymers with low surface energy segments: siloxane- and perfluoroalkane-modified blocks, Polymer, 36, 1321, 10.1016/0032-3861(95)93937-H Jeyaprakash, 2000, A solvent-free method for the synthesis of block copolymers with fluorinated pendant groups by a hydrosilylation reaction, J Polym Sci:Part A: Polym Chem, 38, 1179, 10.1002/(SICI)1099-0518(20000401)38:7<1179::AID-POLA17>3.0.CO;2-L Ren, 2000, Synthesis, characterization, and interaction strengths of difluorocarbene-modified polystyrene-polyisoprene block copolymers, Macromolecules, 33, 866, 10.1021/ma9917085 McHugh, 2002, Solubility of CF2-modified polybutadiene and polyisoprene in supercritical carbon dioxide, Macromolecules, 35, 4653, 10.1021/ma012170h Hillmyer, 2004, Fluorinated amphiphilic block copolymers: combining anionic polymerizationi and selective polymer modification, Macromol Symp, 215, 51, 10.1002/masy.200451105 Ren, 2001, A simple and mild route to highly fluorinated model polymers, Macromolecules, 34, 4780, 10.1021/ma010229e Ren, 2002, Effect of selective perfluoroalkylation on the segregation strength of polystyrene-1,2-polybutadiene block copolymers, Macromolecules, 35, 3889, 10.1021/ma011958x Sugiyama, 2002, Synthesis and surface characterization of novel perfluorooctyl-functionalized polymers with well-defined architectures, Macromol Symp, 181, 135, 10.1002/1521-3900(200205)181:1<135::AID-MASY135>3.0.CO;2-Z Hirao, 2004, Synthesis of well-defined chain-end-functionalized polystyrenes with four, eight, and sixteen perfluorooctyl groups and their surface characterization, Polym Adv Technol, 15, 15, 10.1002/pat.430 Yokoyama, 2004, Surface structure of asymmetric fluorinated block copolymers, Macromolecules, 37, 939, 10.1021/ma035191f Yokoyama, 2004, Surface hydrophobicity of fluorinated block copolymers enhanced by supercritical carbon dioxide annealing, Langmuir, 20, 10001, 10.1021/la0495231 Hirao A, Sugiyama, K. Unpublished results. Schulmanb, 1952, The spreading of liquids on low-energy surfaces. V: perfluorodecanoic acid monolayers, J Colloid Sci, 7, 465, 10.1016/0095-8522(52)90030-5 Nishino, 1999, The lowest surface free energy based on –CF3 alignment, Langmuir, 15, 4321, 10.1021/la981727s Nishino, 2004, Surface properties and structures of diblock and random copolymers with perfluoroalkyl side chains, J Colloid Inter Sci, 279, 364, 10.1016/j.jcis.2004.06.082 Nishino, 2005, Surface properties and structures of diblock and homopolymer with perfluoroalkyl side chains, J Colloid Inter Sci, 283, 533, 10.1016/j.jcis.2004.09.041 Urushihara, 2005, Effects on film-forming conditions on surface properties and structures of diblock copolymer with perfluoroalkyl side chains, Langmuir, 21, 2614, 10.1021/la047317n Muthukumar, 1997, Competing interactions and levels of ordering in self-organizing polymeric materials, Science, 277, 1225, 10.1126/science.277.5330.1225 Yokoyama, 2004, Tunable nanocellular polymeric monoliths using fluorinated block copolymer templates and supercritical carbon dioxide, Adv Mater, 16, 1542, 10.1002/adma.200400072 Krupers, 1998, Micellar morphology of a semifluorinated diblock copolymer, Polym Bull, 40, 211, 10.1007/s002890050244 Imae, 2000, Self-assemblies of block copolymer of 2-perfluorooctylethyl methacrylate and methyl methacrylate, Colloid Surface A: Physcochem Eng Aspects, 167, 73, 10.1016/S0927-7757(99)00484-7 Zhou, 2003, Micellar shape change and internal segregation induced by chemical modification of a tryptych block copolymer surfactant, J Am Chem Soc, 125, 10182, 10.1021/ja036551h Hirao, 2002, Synthesis of novel well-defined chain-end- and in-chain-functionalized polystyrenes with one, two, three, and four perfluorooctyl groups and their surface characterization, Macromolecules, 35, 7642, 10.1021/ma0203187 Sugiyama, 2004, Precise synthesis and surface characterization of well-defined chain-end-functionalized polystyrenes with two, four, eight, sixteen, and thirty-two pefluorooctyl groups, Macroml Symp, 217, 1, 10.1002/masy.200451301 Hirao, 1999, Synthesis of well-defined functionalized polystyrenes with a definite number of chloromethylphenyl groups at chain ends or in chains by means of anionic living polymerization in conjunction with functional group transformation, Macromolecules, 32, 6450, 10.1021/ma990618x Hirao, 2002, Review: precise synthesis of regular and asymmetric star polymers and densely branched polymers with starlike structures by means of living anionic polymerization, Polym J, 34, 633, 10.1295/polymj.34.633 Haraguchi, 2003, Synthesis of well-defined star-linear block polymers by coupling reactions of chain-functionalized polystyrenes with a definite number of benzyl bromide moieties with polystyryllithiums, Macromolecules, 36, 9364, 10.1021/ma034799l Hirao, 2004, Synthesis of chain-end-functionalized polystyrenes with a definite number of benzyl bromide moieties by a novel iterative divergent approach and their synthetic application to well-defined star-branched polymers, Macromol Symp, 13, 69 Hirao, 2005, Precise synthesis of chain-multi-functionalized polymers, star-branched polymers, star-linear block copolymers, densely branched polymers, and dendritic branched polymers based on iterative approach using functionalized 1,1-diphenylethylene derivatives, Prog Polym Sci, 30, 111, 10.1016/j.progpolymsci.2004.12.002 Li, 2004, Multicompartment micelles from ABC miktoarm stars in water, Science, 306, 98, 10.1126/science.1103350 Lodge, 2005, Simultaneous, segregated storage of two agents in a multicompartment micelle, J Am Chem Soc, 127, 17608, 10.1021/ja056841t Six, 1995, From star-shaped to dendritic poly(ethylene oxide)s: toward increasingly branched architectures by anionic polymerization, Macromol Symp, 95, 137, 10.1002/masy.19950950113 Angot, 2000, Amphiphilic stars and dendrimer-like architectures based on poly(ethylene oxide) and polystyrene, Macromolecules, 33, 5418, 10.1021/ma000079s Gnanou, 2001, Stars and dendrimer-like architectures by the divergent method using controlled radical polymerization, Macromol Symp, 174, 333, 10.1002/1521-3900(200109)174:1<333::AID-MASY333>3.0.CO;2-W Percec, 2003, Universal iterative strategy for the divergent synthesis of dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible TERminator multifunctional INItiator (TERMINI), J Am Chem Soc, 125, 6503, 10.1021/ja034746j Matsuo, 2004, Synthesis of well-defined dendrimer-like branched polymers and block copolymer by iterative approach involving coupling reaction of living anionic polymer and functionalization, Macromolecules, 37, 6283, 10.1021/ma0496549 Hirao, 2005, Precise synthesis of dendrimer-like star-branched poly(methyl methacrylate)s up to seventh generation by an iterative divergent approach involving coupling and transformation reactions, Macromolecules, 38, 8701, 10.1021/ma050762k Feng, 2005, Toward an easy access to dendrimer-like poly(ethylene oxide)s, J Am Chem Soc, 127, 10956, 10.1021/ja0509432 Hutchings, 2006, DendriMacs: well-defined dendritically branched polymers synthesized by an iterative convergent strategy involving the coupling reaction of AB2 macromonomers, Macromolecules, 39, 2144, 10.1021/ma052627d Orfanou, 2006, Synthesis of well-defined second (G-2) and third (G-3) generation dendritic polybutadienes, Macromolecules, 39, 4361, 10.1021/ma060231b Watanabe, 2006, Synthesis of dendrimer-like star-branched poly(methyl methacrylate)s of generations consisting of four branched polymer chains at each junction by iterative methodology involving coupling and transformation reactions, Macromol Symp, 240, 23, 10.1002/masy.200650804 Hirao, 2006, Highlight article: precise synthesis of well-defined dendrimer-like star-branched polymers by iterative methodology based on living anionic polymerization, J Polym Sci: Part A: Polym Chem, 44, 6659, 10.1002/pola.21701 Hirao, 2006, Precise synthesis of dendron-like hyperbranched polymers and block copolymers by an iterative approach involving living anionic polymerization, coupling reaction, and transformation reaction, Macromol Res, 14, 272, 10.1007/BF03219083 Hirao A, Sugiyama K, Matsuo A, Tsunoda Y, Watanabe T. Synthesis of well-defined dendritic hyperbranched polymers by iterative methodologies using living/controlled polymerizations. Polym Int 2007;56: in press. Matyjaszewski, 2001, Atom transfer radical polymerization, Chem Rev, 101, 2921, 10.1021/cr940534g Kamigaito, 2001, Metal-catalyzed living radical polymerization, Chem Rev, 101, 3689, 10.1021/cr9901182 Hadjichristidis, 2001, Polymers with comlex architecture by living anionic polymerization, Chem Rev, 101, 3747, 10.1021/cr9901337