Skip to main content
SpringerLink
Log in

Block Copolymers by Anionic Polymerization: Recent Synthetic Routes and Developments

  • Chapter
Anionic Polymerization

Abstract

Anionic polymerization is the method of choice for the synthesis of well-defined block copolymers characterized by molecular and chemical homogeneity. The applicability of the method has been expanded from the classical monomers, such as styrenes, dienes, methacrylates, acrylates, ethylene oxide, and vinyl pyridines, to a broader range of monomers, such as methacrylates with bulky or functional ester groups, lactones, hexamethylcyclotrisiloxane, 1,3-cyclohexadiene, isocyanates, metal-containing monomers, etc. Recent advances regarding the synthesis of linear block copolymers (e.g., AB diblocks, ABA and ABC triblocks, ABCD tetrablocks, (AB)n multiblocks) will be presented in this chapter.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 259.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 329.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 329.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Riess G, Hurtrez G, Bahadur P (1985) Block copolymers. In: Mark HF, Bikales NM, Overberger CG, Menges G, Kroschwitz JI (eds) Encyclopedia of polymer science and engineering, vol 2, 2nd edn. Wiley, New York, pp 324–434

    Google Scholar 

  2. (a) Hamley IW (1998) The physics of block copolymers. Oxford University Press, Oxford; (b) Abetz V, Simon PFW (2005) Phase behavior and morphologies of block copolymers. Adv Polym Sci 189:125–212; (c) Hamley IW (ed) (2004) Developments in block copolymer science and technology. John Wiley & Sons, Chichester; (d) Bates FM, Fredrickson GH (1990) Block copolymer thermodynamics: theory and experiment. Ann Rev Phys Chem 41:525–557

    Google Scholar 

  3. (a) Gohy JF (2005) Block copolymer micelles. Adv Polym Sci 190:65–136; (b) Riess G (2003) Micellization of block copolymers. Prog Polym Sci 28:1107–1170

    Google Scholar 

  4. (a) Torchilin VP (2001) Structure and design of polymeric surfactant-based drug delivery systems. J Control Release 73:137–172; (b) Kataoka K, Harada A, Nagasaki Y (2001) Block copolymer micelles for drug delivery: design, characterization and biological significance. Adv Drug Deliv Rev 47:113–131; (c) Kabanov AV, Batrakova EV, Alakhov VY (2002) Pluronic® block copolymers as novel polymer therapeutics for drug and gene delivery. J Control Release 82:189–212; (d) Kakizawa Y, Kataoka K (2002) Block copolymer micelles for delivery of gene and related compounds. Adv Drug Deliv Rev 54:203–222; (e) Munch MR, Gast AP (1990) Kinetics of block copolymer adsorption on dielectric surfaces from a selective solvent. Macromolecules 23:2313–2320; (f) Xu R, d’ Oliveira JMR, Winnik MA, Riess G, Croucher MD (1992) Characterization of block copolymer micelles and their adsorption onto latex particles. Appl Polym Symp Ser 51:135–149; (g) Breulman M, Förster S, Antonietti M (2000) Mesoscopic surface patterns formed by block copolymer micelles. Macromol Chem Phys 201:204–211; (h) Cao T, Yin W, Armstrong JL, Webber SE (1994) Adsorption of photoactive amphiphilic polymers onto hydrophobic polymer films: polystyrene-block-poly(2-vinylnaphthalene)-block-poly(methacrylic acid). Langmuir 10:1841–1847; (i) Spatz JP, Sheiko S, Möller M (1996) Ion-stabilized block copolymer micelles: film formation and intermicellar interaction. Macromolecules 29:3220–3226

    Google Scholar 

  5. (a) Hsieh HL, Quirk RP (1996) Anionic polymerization. Principles and practical applications. Marcel Dekker, New York; (b) Hong K, Urhig D, Mays JW (1999) Living anionic polymerization. Curr Opin Solid State Mater Sci 4:531–538

    Google Scholar 

  6. (a) Hadjichristidis N, Pitsikalis M, Pispas S, Iatrou H (2001) Polymers with complex architecture by living anionic polymerization. Chem Rev 101:3747–3792. doi:10.1021/cr9901337; (b) Hadjichristidis N, Pitsikalis M, Pispas S, Iatrou H (2001) Polymers with complex architectures by living anionic polymerization. Chem Rev 101:3747–3792

  7. (a) Hadjichristidis N, Iatrou H, Pispas S, Pitsikalis M (2000) Anionic polymerization: high vacuum techniques. J Polym Sci Polym Chem Ed 38:3211–3234; (b) Uhrig D, Mays JW (2005) Experimental techniques in high-vacuum anionic polymerization. J Polym Sci Polym Chem Ed 43:6179–6222

    Google Scholar 

  8. (a) Hadjichristidis N, Pispas S, Floudas GA (2003) Block copolymers. Synthetic strategies, physical properties and applications. Wiley, Hoboken; (b) Pitsikalis M, Pispas S, Mays JW, Hadjichristidis N (1998) Nonlinear block copolymer architectures. Adv Polym Sci 135:1; (c) Lodge TP (2003) Block copolymers: past successes and future challenges. Macromol Chem Phys 204:265–273

    Google Scholar 

  9. Hadjichristidis N, Pispas S, Iatrou H, Pitsikalis M (2002) Linking chemistry and anionic polymerization. Curr Org Chem 6:155–176

    Article  CAS  Google Scholar 

  10. Pitsikalis M, Sioula S, Pispas S, Hadjichristidis N, Cook DC, Li J, Mays JW (1999) Linking reactions of living polymers with bromomethylbenzene derivatives: synthesis and characterization of star homopolymers and graft copolymers with polyelectrolyte branches. J Polym Sci Polym Chem Ed 37:4337–4350

    Article  CAS  Google Scholar 

  11. (a) Guyot P, Favier JC, Fontanille M, Sigwalt P (1982) New perfectly difunctional organolithium initiators for block copolymer synthesis: 2. Difunctional polymers of dienes and of their triblocks copolymers with styrene. Polymer 23:73–76; (b) Tung LH, Lo GYS (1994) Hydrocarbon-soluble di- and multifunctional organolithium initiators. Macromolecules 27:1680–1684; (c) Tung LH, Lo GYS (1994) Studies on dilithium initiators. 1. Hydrocarbon-soluble initiators 1,3-phenylenebis(3-methyl-1-phenylpentylidene)dilithium and 1,3-phenylenebis[3-methyl-1-(methylphenyl) pentylidene]dilithium. Macromolecules 27:2219–2224; (d) Bandemann F, Speikamp HD, Weigel L (1985) Bifunctional anionic initiators: a critical study and overview. Makromol Chem 186:2017–2024; (e) Vasilakopoulos T, Hadjichristidis N (2013) Influence of (1,3-phenylene)bis(3-methyl-1-phenyl pentylidene)dilithium initiator concentration on the modality of polybutadiene. J Polym Sci Part A Polym Chem 51:824–835

    Google Scholar 

  12. (a) Bates FM, Fredrickson GH (1990) Block copolymer thermodynamics: theory and experiment. Ann Rev Phys Chem 41:525–557; (b) Hadjichristidis N, Iatrou H, Pitsikalis M, Pispas S, Avgeropoulos A (2005) Linear and non-linear multiblock terpolymers. Synthesis, self-assembly in selective solvents and in bulk. Prog Polym Sci 30:725–782

    Google Scholar 

  13. McGrath MP, Sall ED, Tremont SJ (1995) Functionalization of polymers by metal-mediated processes. Chem Rev 95:381–398

    Article  CAS  Google Scholar 

  14. Lehn J-M (1995) Supramolecular chemistry, concepts and perspectives. VCH, Weinheim

    Book  Google Scholar 

  15. Schubert US, Eschbaumer C (2002) Macromolecules containing bipyridine and terpyridine metal complexes: towards metallosupramolecular polymers. Angew Chem Int Ed 41:2892–2926

    Article  CAS  Google Scholar 

  16. (a) Lohmeijer BGG, Schubert US (2003) Playing LEGO with macromolecules: design, synthesis, and self-organization with metal complexes. J Polym Sci Polym Chem Ed 41:1413–1427; (b) Andres PR, Schubert US (2004) New functional polymers and materials based on 2,2’:6’,2”-terpyridine metal complexes. Adv Mater 16:1043–1068

    Google Scholar 

  17. Gohy J-F, Lohmeijer BGG, Schubert US (2002) Metallo-supramolecular block copolymer micelles. Macromolecules 35:4560–4563

    Article  CAS  Google Scholar 

  18. Gohy J-F, Lohmeijer BGG, Schubert US (2002) Reversible metallo-supramolecular block copolymer micelles containing a soft core. Macromol Rapid Commun 23:555–560

    Article  CAS  Google Scholar 

  19. Gohy J-F, Lohmeijer BGG, Varshney SK, Décamps B, Leroy E, Boileau S, Schubert US (2002) Stimuli-responsive aqueous micelles from an ABC metallo-supramolecular triblock copolymer. Macromolecules 35:9748–9755

    Article  CAS  Google Scholar 

  20. (a) Morton M (1983) Anionic polymerization: principles and practise. Academic Press, New York; (b) Fetters LJ, Morton M (1969) Synthesis and properties of block copolymers. I. Poly α-methylstyrene-polyisoprene-poly-α-methyl styrene. Macromolecules 2:453–458; (c) Fetters LJ, Firer EM, Dafauti EM (1977) Macromolecules 10:1200–1207; (d) Corbin N (1976) Prud’homme J. J Polym Sci Part A Polym Chem 14:1645–1659; (e) Quirk RP, Lee R (1992) Experimental criteria for living polymerizations. Polym Int 27:359–367

    Google Scholar 

  21. (a) Natori I (1997) Synthesis of polymers with an alicyclic structure in the main chain. Living anionic polymerization of 1,3-cyclohexadiene with the n-butyllithium/N,N,N‘,N‘-tetramethyl- ethylenediamine system. Macromolecules 30:3696–3697; (b) Natori I, Inoue S (1998) Living anionic polymerization of 1,3-cyclohexadiene with the n-butyllithium/N,N,N‘,N‘-tetramethylethylenediamine system. Copolymerization and block copolymerization with styrene, butadiene, and isoprene. Macromolecules 31:982–987; (c) Natori I, Inoue S (1998) Anionic polymerization of 1,3-cyclohexadiene with alkyllithium/amine systems. Characteristics of n-butyllithium/N,N,N‘,N‘-tetramethylethylenediamine system for living anionic polymerization. Macromolecules 31:4687–4694

    Google Scholar 

  22. (a) Natori I, Imaizumi K, Yamagishi H, Kazunori M (1998) Hydrocarbon polymers containing six-membered rings in the main chain. Microstructure and properties of poly(1,3-cyclohexadiene). J Polym Sci Part B Polym Phys 36:1657–1668; (b) Natori I, Imaizumi K (2000) Synthesis of novel hydrocarbon polymers containing 6-membered rings in the main chain: living anionic polymerization of 1,3-cyclohexadiene. Macromol Symp 157:143–150

    Google Scholar 

  23. Natori I, Inoue S (1998) Anionic polymerization of 1,3-cyclohexadiene with alkyllithium/amine systems. Characteristics of n-butyllithium/N, N, N‘, N‘-tetramethylethylenediamine system for living anionic polymerization. Macromolecules 31:4687–4694

    Article  CAS  Google Scholar 

  24. Imaizumi K, Ono T, Natori I, Sakurai S, Takeda K (2000) Microphase-separated structure of 1,3-cyclohexadiene/butadiene triblock copolymers and its effect on mechanical and thermal properties. J Polym Sci Polym Phys Ed 39:13–22

    Article  Google Scholar 

  25. Hong K, Mays JW (2001) 1,3-cyclohexadiene polymers. 3. Synthesis and characterization of poly(1,3-cyclohexadiene-block-styrene). Macromolecules 34:3540–3547

    Article  CAS  Google Scholar 

  26. Tsoukatos T, Avgeropoulos A, Hadjichristidis N, Hong K, Mays JW (2002) Model linear block co-, ter-, and quaterpolymers of 1,3-cyclohexadiene with styrene, isoprene, and butadiene. Macromolecules 35:7928–7935

    Article  CAS  Google Scholar 

  27. Williamson DT, Buchanan TD, Elkins CL, Long TE (2004) Synthesis of block copolymers based on the alternating anionic copolymerization of styrene and 1,3-cyclohexadiene. Macromolecules 37:4505–4511

    Article  CAS  Google Scholar 

  28. Natori I, Natori S, Sato H (2006) Soluble polyphenylene homopolymers with controllable microstructure and properties: optical and electrical characteristics of completely dehydrogenated poly(1,3-cyclohexadiene) as a π-conjugated polymer semiconductor. Polymer 47:7123–7130

    Article  CAS  Google Scholar 

  29. Natori I, Natori S, Sekikawa H, Takahashi T, Ogino K, Tsuchiya K, Sato H (2010) Poly(4-diphenylaminostyrene) with a well-defined polymer chain structure: controllable optical and electrical properties. Polymer 51:1501–1506

    Article  CAS  Google Scholar 

  30. Natori I, Natori S, Sekikawa H, Tsuchiya K, Ogino K (2011) Synthesis of poly(p-phenylene)-poly(4-diphenylaminostyrene) bipolar block copolymers with a well-controlled and defined polymer chain structure. J Polym Sci Part A Polym Chem 49:1655–1663

    Article  CAS  Google Scholar 

  31. Natori I, Natori S, Sekikawa H, Sato H (2008) Synthesis of soluble poly(para-phenylene) with a long polymer chain: characteristics of regioregular poly(1,4-phenylene). J Polym Sci Part A Polym Chem 46:5223–5231

    Article  CAS  Google Scholar 

  32. Natori I, Natori S, Usui H, Sato H (2008) Anionic polymerization of 4-diphenylaminostyrene: characteristics of the alkyllithium/N, N, N’, N’-tetramethylethylenediamine system for living anionic polymerization. Macromolecules 41:3852–3858

    Article  CAS  Google Scholar 

  33. Natori I, Natori S (2011) Ultrasound-accelerated dehydrogenation of poly(1,3-cyclohexadiene): efficient synthesis of poly(para-phenylene). Polym Int 60:543–548

    Article  CAS  Google Scholar 

  34. Harada M, Suzuki T, Ohya M, Kawaguchi D, Takano A, Matsushita Y (2005) Novel miscible polymer blend of poly(4-trimethylsilylstyrene) and polyisoprene. Macromolecules 38:1868–1873

    Article  CAS  Google Scholar 

  35. Gladkova N, Durgar’yan S (1984) Synthesis of the AB type block copolymers (polyvinyltrimethylsilane-polydimethylsiloxane). Polym Sci USSR 26(7):1642–1648

    Article  Google Scholar 

  36. Durgar’yan S, Filippova V (1986) Synthesis and properties of three-block copolymers poly(dimethylsiloxane)-poly(vinyltrimethylsilane)-poly(dimethyl-siloxane). Polym Sci USSR 28(2):364–370

    Article  Google Scholar 

  37. Filippova V, Nametkin N, Durgar’yan S (1966) Copolymerization of vinyltrimethylsilane with styrene in the presence of butyllithium. Russ Chem Bull 15(10):1670–1673

    Article  Google Scholar 

  38. Rangou S, Shishatskiy S, Filiz V, Abetz V (2011) Poly(vinyl trimethylsilane) and block copolymers of vinyl trimethylsilane with isoprene: anionic polymerization, morphology and gas transport properties. Eur Polym J 47:723–729

    Article  CAS  Google Scholar 

  39. Mays J, Hadjichristidis N (1988) Characteristic ratios of polymethacrylates. J Macromol Sci C 28:371

    Article  Google Scholar 

  40. (a) Baskaran D, Müller AHE (2006) Anionic vinyl polymerization – 50 years after Michael Szwarc. Progr Polym Sci 31:173–219; (b) Mori H, Müller AHE (2008) New polymeric architectures with (meth)acrylic segments. Prog Polym Sci 10:1403–1439

    Google Scholar 

  41. Varshney SK, Hautekeer JP, Fayt R, Jérôme P, Teyssié P (1990) Anionic polymerization of (meth)acrylic monomers. 4. Effect of lithium salts as ligands on the “living” polymerization of methyl methacrylate using monofunctional initiators. Macromolecules 23:2618–2622

    Article  CAS  Google Scholar 

  42. (a) Vlček P, Lochmann L (1999) Anionic polymerization of (meth)acrylate esters in the presence of stabilizers of active centres. Prog Polym Sci 24:793–873; (b) Lochmann L, Kolařík J, Doskočilová D, Vozka S, Trekoval J (1979) Metallo esters. VII. Stabilizing effect of sodium tert-butoxide on the growth center in the anionic polymerization of methacrylic esters. J Polym Sci Polym Chem Ed 17:1727–1737; (c) Vlček P, Lochmann L, Otoupalová J (1992) The anionic polymerization of acrylates, 4 the polymerization of 2-ethylhexyl acrylate initiated with a mixed initiator lithium ester-enolate/lithium tert-butoxide. Makromol Chem Rapid Commun 13:163–167

    Google Scholar 

  43. (a) Bayard P, Jérôme R, Teyssié RPh, Varshney SK, Wang JS (1994) A new family of “ligated” anionic initiators for the “living” polymerization of (meth)acrylic esters. Polym Bull 32:381–385; (b) Nugay N, Nugay T, Jérôme R, Teyssié Ph (1997) Anionic polymerization of primary acrylates as promoted by lithium 2-(2-methoxyethoxy) ethoxide. J Polym Sci Part A Polym Chem 35:361–369; (c) Baskaran D (2000) Living anionic polymerization of methyl methacrylate in the presence of polydentate dilithium alkoxides. Macromol Chem Phys 201:890–895

    Google Scholar 

  44. Baskaran D, Sivaram S (1997) Specific salt effect of lithium perchlorate in living anionic polymerization of methyl methacrylate and tert-butyl acrylate. Macromolecules 30:1550–1555

    Article  CAS  Google Scholar 

  45. Zundel T, Teyssié P, Jérôme R (1998) New ligands for the living isotactic anionic polymerization of methyl methacrylate in toluene at 0 °C. 1. Ligation of butyllithium by lithium silanolates. Macromolecules 31:2433–2439

    Article  CAS  Google Scholar 

  46. (a) Tong JD, Jerôme R (2000) Synthesis of poly(methyl methacrylate)-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate) triblocks and their potential as thermoplastic elastomers. Polymer 41:2499–2510; (b) Tong JD, Leclére P, Doneux C, Brédas JL, Lazzaroni R, Jerôme R (2000) Synthesis and bulk properties of poly(methyl methacrylate)-b-poly(isooctyl acrylate)-b-poly(methyl methacrylate). Polymer 41:4617–4624

    Google Scholar 

  47. (a) Pitsikalis M, Siakali-Kioulafa E, Hadjichristidis N (2000) Block copolymers of styrene and stearyl methacrylate. Synthesis and micellization properties in selective solvents. Macromolecules 33:5460–5469; (b) Pitsikalis M, Siakali-Kioulafa E, Hadjichristidis N (2004) Block copolymers of styrene and n-alkyl methacrylates with long alkyl groups. Micellization behavior in selective solvents. J Polym Sci Polym Chem Ed 42:4177–4188

    Google Scholar 

  48. Allen RD, Long TE, McGrath JE (1986) Preparation of high purity, anionic polymerization grade alkyl methacrylate monomers. Polym Bull 15:127–134

    Article  CAS  Google Scholar 

  49. Černoch P, Štěpánek P, Pleštil P, Šlouf M, Sidorenko A, Stamm M (2007) Surface patterns of block copolymers in thin layers after vapor treatment. Eur Polym J 43:1144–1153

    Article  CAS  Google Scholar 

  50. Kennemur J, Hillmyer M, Bates F (2012) Synthesis, thermodynamics, and dynamics of poly(4-tertbutylstyrene-b-methylmethacrylate). Macromolecules 45:7228–7236

    Article  CAS  Google Scholar 

  51. Imae T, Tabuchi H, Funayama K, Sato A, Nakamura T, Amaya N (2000) Self-assemblies of block copolymer of 2-perfluorooctylethyl methacrylate and methyl methacrylate. Colloids Surf A 167:73–81

    Article  CAS  Google Scholar 

  52. Busse K, Kressler J, van Eck D, Höring S (2002) Synthesis of amphiphilic block copolymers based on tert-butyl methacrylate and 2-(N-methylperfluorobutane sulfonamido) ethyl methacrylate and its behavior in water. Macromolecules 35:178–184

    Article  CAS  Google Scholar 

  53. Xiong D, Liu G, Hong L, Duncan S (2011) Superamphiphobic diblock copolymer coatings. Chem Mater 23:4357–4366

    Article  CAS  Google Scholar 

  54. Maeda R, Hayakawa T, Ober CK (2012) Dual mode patterning of fluorine-containing block copolymers through combined top-down and bottom-up lithography. Chem Mater 24:1454–1461

    Article  CAS  Google Scholar 

  55. Jie X, Peihong N, Jiang M (2006) Synthesis and characterization of a novel triblock copolymer containing double-hydrophilic blocks and poly(fluoroalkyl methacrylate) block via oxyanioninitiated polymerization. e-Polymers no. 015. ISSN 1618–7229

    Google Scholar 

  56. Lin X, Deng L, Dong A (2012) Synthesis of fluorescent methoxy poly(ethylene glycol)-b-poly(ethyl cyanoacrylate)–2-(N-carbazolyl)ethyl methacrylate copolymer via living oxyanion-initiated polymerization. J Appl Polym Sci 123:3575–3579

    Article  CAS  Google Scholar 

  57. Ishizone T, Tajima H, Torimae H, Nakahama S (2002) Anionic polymerizations of 1-adamantyl methacrylate and 3-methacryloyloxy-1,1’-biadamantane. Macromol Chem Phys 203:2375–2384

    Article  CAS  Google Scholar 

  58. (a) De Paz Bàñez M, Robinson K, Armes S (2001) Use of oxyanion-initiated polymerization for the synthesis of amine methacrylate-based homopolymers and block copolymers. Polymer. 42:29–37;(b) Ni P, Zhang M, Ma L, Fu S (2006) Poly(dimethylamino)ethyl methacrylate for use as a surfactant in the miniemulsion polymerization of styrene. Langmuir 22:6016–6023

    Google Scholar 

  59. Schacher F, Müllner M, Schmalz H, Müller A (2009) New block copolymers with poly(N, N-dimethylaminoethyl methacrylate) as a double stimuli-responsive block. Macromol Chem Phys 210:256–262

    Article  CAS  Google Scholar 

  60. Chen S, Kuo S, Liao S, Chang F (2008) Syntheses, specific interactions, and pH-sensitive micellization behavior of poly[vinylphenol-b-2-(dimethylamino)ethyl methacrylate] diblock copolymers. Macromolecules 41:8865–8876

    Article  CAS  Google Scholar 

  61. Mountrichas G, Pispas S (2006) Synthesis and pH responsive self-assembly of new double hydrophilic block copolymers. Macromolecules 39:4767–4774

    Article  CAS  Google Scholar 

  62. Lehmann O, Förster S, Springer J (2000) Synthesis of new side-group liquid crystalline block copolymers by living anionic polymerization. Macromol Rapid Commun 21:133–135

    Article  CAS  Google Scholar 

  63. Zhang H, Ruckestein E (2001) Novel monodisperse functional (co)polymers based on the selective living anionic polymerization of a new bifunctional monomer, trans, trans-1-methacryloyloxy-2,4-hexadiene. Macromolecules 34:3587–3593

    Article  CAS  Google Scholar 

  64. Ishizone T, Han S, Okuyama S, Nakahama S (2003) Synthesis of water-soluble polymethacrylates by living anionic polymerization of trialkylsilyl-protected oligo(ethylene glycol) methacrylates. Macromolecules 36:42–49

    Article  CAS  Google Scholar 

  65. (a) Hirai T, Leolukman M, Hayakawa T, Kakimoto M, Gopalan P (2008) Hierarchical nanostructures of organosilicate nanosheets within self-organized block copolymer films. Macromolecules 41:4558–4560; (b) Hirai T, Leolukman M, Jin S, Goseki R, Ishida Y, Kakimoto M, Hayakawa T, Ree M, Gopalan P (2009) Hierarchical self-assembled structures from POSS-containing block copolymers synthesized by living anionic polymerization. Macromolecules 42(22):8835–8843

    Google Scholar 

  66. Sugiyama K, Oie T, El-Magd A, Hirao A (2010) Synthesis of well-defined (AB)n multiblock copolymers composed of polystyrene and poly(methyl methacrylate) segments using specially designed living AB diblock copolymer anion. Macromolecules 43:1403–1410

    Article  CAS  Google Scholar 

  67. Hirao A, Matsuo Y, Oie T, Goseki R, Ishizone T (2011) Facile synthesis of triblock co- and terpolymers of styrene, 2-vinylpyridine, and methyl methacrylate by a new methodology combining living anionic diblock copolymers with a specially designed linking reaction. Macromolecules 44:6345–6355

    Article  CAS  Google Scholar 

  68. Matsuo Y, Oie T, Goseki R, Ishizone T, Sugiyama K, Hirao A (2013) Precise synthesis of new triblock co- and terpolymers by a methodology combining living anionic polymers with a specially designed linking reaction. Macromol Symp 323:26–36

    Article  CAS  Google Scholar 

  69. (a) Busfield W, Mathwen J (1973) Anionic polymerization of methyl acrylate. Polymer 14:137–144; (b) Kitano T, Fujimoto T, Nagasawa M (1997) Anionic polymerization of tert-butyl. Acrylate Polym J 9:153–159

    Google Scholar 

  70. (a) Wang J, Jérôme R, Bayard P, Teyssié Ph (1995) Anionic polymerization of acrylic monomers. 21. Anionic sequential polymerization of 2-ethylhexyl acrylate and methyl methacrylate. Macromolecules 27:4908–4913; (b) Nugay N, Nugay T, Jérôme R, Teyssié Ph (1997) Ligated anionic block copolymerization of methyl methacrylate with n-butyl acrylate and n-nonyl acrylate as promoted by lithium 2-(2-methoxyethoxy) ethoxide/diphenylmethyllithium. J Polym Sci Part A Polym Chem 35:1543–1548

    Google Scholar 

  71. Vlček P, Otoupalová J, Sikora A, Kříž J (1995) Anionic polymerization of acrylates. 10. Synthesis and characterization of block copolymers with acrylate blocks. Macromolecules 28:7262–7265

    Article  Google Scholar 

  72. Vlček P, Čadová E, Kříž J, Látalová P, Janata M, Toman L, Masař B (2005) Anionic polymerization of acrylates. XIV. Synthesis of MMA/acrylate block copolymers initiated with ester-enolate/tert-alkoxide complex. Polymer 46:4991–5000

    Article  CAS  Google Scholar 

  73. Xie X, Hogen-Esch T (1996) Anionic synthesis of narrow molecular weight distribution water-soluble poly(N, N-dimethylacrylamide) and poly(N-acryloyl-N ‘-methylpiperazine). Macromolecules 29:1746–1752

    Article  CAS  Google Scholar 

  74. (a) Kobayashi M, Okuyama S, Ishizone T, Nakahama S (1999) Stereospecific anionic polymerization of N,N-dialkylacrylamides. Macromolecules 32:6466–6477; (b) Kobayashi M, Ishizone T, Nakahama S (2000) Synthesis of highly isotactic poly(N,N-diethylacrylamide) by anionic polymerization with grignard reagents and diethylzinc. J Polym Sci Part A Polym Chem 38:4677–4685

    Google Scholar 

  75. André X, Zhang M, Müller A (2005) Thermo- and pH-responsive micelles of poly(acrylic acid)-block-poly(N, N-diethylacrylamide). Macromol Rapid Commun 26:558–563

    Article  CAS  Google Scholar 

  76. Vinogradova L, Fedorova L, Adler H-J, Kuckling D, Seifert D, Tsvetanov C (2005) Controlled anionic block copolymerization with N, N-dialkylacrylamide as a second block. Macromol Chem Phys 206:1126–1133

    Article  CAS  Google Scholar 

  77. Kobayachi M, Chiba T, Tsuda K, Takeishi M (2005) Anionic polymerization of N, N-dialkylacrylamides containing alkoxysilyl groups in the presence of Lewis acids. J Polym Sci Part A Polym Chem 43:2754–2764

    Article  CAS  Google Scholar 

  78. Angelopoulos S, Tsitsilianis C (2006) Thermo-reversible hydrogels based on poly(N, N-diethylacrylamide)-block-poly(acrylic acid)-block-poly(N, N-diethylacrylamide) double hydrophilic triblock copolymer. Macromol Chem Phys 207:2188–2194

    Article  CAS  Google Scholar 

  79. (a) Tardi M, Sigwalt P (1972) Etude spectrophotometrique de la reaction d’amorcage de la polymerisation anionique de la vinyl-2 pyridine. Eur Polym J 8:137–149; (b) Tardi M, Sigwalt P (1972) Etude de la conductivite des solutions carbanioniques de poly(vinyl-2, pyridine) dans le tetrahydrofuranne. Eur Polym J 8:151–162; (c) Tardi M, Sigwalt P (1973) Etude de la nature des especes ioniques intervenant au cours de la polymerisation anionique de la vinyl-4 pyridine. Eur Polym J 9:1369–1379; (d) Chang C, Hogen-Esch T (1975) Anionic polymerization of polar monomers. I. Ultraviolet–visible spectroscopic and conductometric studies of ion pairs of alkali salts of vinyl 2-, 3-, and 4-pyridine-type carbanions and their crown ether complexes in aprotic media. J Am Chem Soc 97:2805–2810; (e) Meverden C, Hogen-Esch T (1984) Oligomerization of vinyl monomers, 19. Studies of side reactions occurring in oligomeric models of “living” poly(2-vinylpyridine). Makromol Chem Rapid Commun 5:749–757; (f) Krasnoselskaya I, Erussalimsky B (1985) Non-trivial auto-modification of the active centres in the poly(2-vinylpyridyl)lithium/toluene system. Makromol Chem Rapid Commun 6:191–195; (g) Krasnoselskaya I, Erussalimsky B (1986) Automodification of poly(2-vinylpyridyl)lithium and its consequences for the block copolymerization processes. Acta Polym 37:72–75; (h) Luxton A, Quig A, Delvaux MJ, Fetters L (1978) Star-branched polymers: 2. Linking reaction involving 2- and 4-vinyl pyridine and dienyland styryllithium chain ends. Polymer 19:1320–1324; (i) Varshney S, Zhong X, Eisenberg A (1993) Anionic homopolymerization and block copolymerization of 4-vinylpyridine and its investigation by high-temperature size-exclusion chromatography in N-methyl-2-pyrrolidinone. Macromolecules 26:701–706; (j) Watanabe H, Shimura T, Kotaka T, Tirrell M (1993) Synthesis, characterization, and surface structures of styrene-2-vinylpyridine-butadiene three-block polymers. Macromolecules 26:6338–6345

    Google Scholar 

  80. (a) Quirk RP, Galvan-Corona S (2001) Controlled anionic synthesis of polyisoprene−poly(2-vinylpyridine) diblock copolymers in hydrocarbon solution. Macromolecules 34:1192–1197; (b) Tsitsilianis C, Sfika V (2001) Heteroarm star-like micelles formed from polystyrene-block-poly(2-vinyl pyridine)-block-poly(methyl methacrylate) ABC triblock copolymers in toluene. Macromol Rapid Commun 22:647–651

    Google Scholar 

  81. Möller M, Lenz R (1989) Poly(2-vinylpyridine) block copolymers. Phase separation and electric conductivity of iodine complexes. Makromol Chem 190:1153–1163

    Article  Google Scholar 

  82. (a) Ludwigs S, Böker A, Abetz V, Müller A, Krausch G (2003) Phase behavior of linear polystyrene-block-poly(2-vinylpyridine)-block-poly(tert-butyl methacrylate) triblock terpolymers. Polymer 44:6815–6823; (b) Giebeler E, Stadler R (1997) ABC triblock polyampholytes containing a neutral hydrophobic block, a polyacid and a polybase. Macromol Chem Phys 198:381–38255; (c) Watanabe H, Amemiya T, Shimura T, Kotaka T (1994) Anionic synthesis of graft block copolymers with poly(2-vinylpyridine) trunks: effects of trunk and branch molecular weights. Macromolecules 27:2336–2338; (d) Watanabe H, Shimura T, Kotaka T, Tirrell M (1993) Synthesis, characterization, and surface structures of styrene-2-vinylpyridine-butadiene three-block polymers. Macromolecules 26:6338–6345

    Google Scholar 

  83. (a) Shin YD, Han SH, Samal S, Lee JS (2005) Synthesis of poly(2-vinyl pyridine)-b-poly(n-hexyl isocyanate) amphiphilic coil-rod block copolymer by anionic polymerization. J Polym Sci Part A Polym Chem 43:607–615; (b) Isaacs N (1987) Physical organic chemistry. Longman House, Essex, p 136

    Google Scholar 

  84. (a) Schultz M, Khandpur A, Bates F, Almdal K, Mortensen K, Hajduk D, Gruner S (1966) Phase behavior of polystyrene−poly(2-vinylpyridine) diblock copolymers. Macromolecules 29:2857–2867; (b) Schultz M, Bates F, Almdal K, Mortensen K (1994) Epitaxial relationship for hexagonal-to-cubic phase transition in a book copolymer mixture. Phys Rev Lett 73:86–89; (c) Shull K, Kramer E, Hadziioannou G, Tang W (1990) Segregation of block copolymers to interfaces between immiscible homopolymers. Macromolecules 23:4780–4787; (d) Ruokolainen J, Makinen R, Torkkeli M, Makela T, Serimaa R, ten Brinke G, Ikkala O (1998) Switching supramolecular polymeric materials with multiple length scales. Science 280:557–560; (e) Rukolainen J, Torkkeli M, Serimaa R, Komanschek E, ten Brinke G, Ikkala O (1997) Order–disorder transition in comblike block copolymers obtained by hydrogen bonding between homopolymers and end-functionalized oligomers: poly(4-vinylpyridine)−pentadecylphenol. Macromolecules 30:2002–2007

    Google Scholar 

  85. (a) Sohn B, Seo B (2001) Fabrication of the multilayered nanostructure of alternating polymers and gold nanoparticles with thin films of self-assembling diblock copolymers. Chem Mater 13:1752–1757; (b) Yun S, Yoo S, Jung C, Zin W, Sohn B (2006) Highly ordered arrays of nanoparticles in large areas from diblock copolymer micelles in hexagonal self-assembly. Chem Mater 18:5646–5648

    Google Scholar 

  86. de Moel K, Alberda van Ekenstein G, Nijland H, Polushkin E, ten Brinke G (2001) Polymeric nanofibers prepared from self-organized supramolecules. Chem Mater 13:4580

    Article  CAS  Google Scholar 

  87. Valkama S, Kosonen H, Ruokolainen J, Haatainen T, Torkkeli M, Serimaa R, ten Brinke G, Ikkala O (2004) Self-assembled polymeric solid films with temperature-induced large and reversible photonic-bandgap switching. Nat Mater 3:872–876

    Article  CAS  Google Scholar 

  88. Mantzaridis C, Pispas S (2011) Poly[(sodium sulfamate/carboxylate)isoprene-b-2-vinyl pyridine] block polyampholytes: synthesis and self-assembly in aqueous media. J Polym Sci Part A Polym Chem 49:3090–3098

    Article  CAS  Google Scholar 

  89. Kuo S-W, Tung P-H, Chang F-C (2006) Synthesis and the study of strongly hydrogen-bonded poly(vinylphenol-b-vinylpyridine) diblock copolymer through anionic polymerization. Macromolecules 39:9388–9395

    Article  CAS  Google Scholar 

  90. (a) Varshney S, Zhong X, Eisenberg A (1993) Anionic homopolymerization and block copolymerization of 4-vinylpyridine and its investigation by high-temperature size-exclusion chromatography in N-methyl-2-pyrrolidinone. Macromolecules 26:701–706; (b) Quirk R, Corona-Galvan S (2001) Controlled anionic synthesis of polyisoprene- poly(2-vinylpyridine) diblock copolymers in hydrocarbon solution. Macromolecules 34:1192–1197; (c) Biggs S, Vincent B (1992) Poly(styrene-b-2-vinylpyridine-1-oxide) and poly(dimethylsiloxane-b-2 vinylpyridine-1-oxide) diblock copolymers. 1. Preparation and characterization. Colloid Polym Sci 270:505–510; (d) Hubert P, Soum A, Fontanille M (1995) Structure and reactivity of propagating species in anionic polymerization of 2-vinylpyridine initiated by lithium derivatives in toluene. Macromol Chem Phys 196:1023–1030; (e) Quirk RP, Lee Y (2000) Oligomerization of 1,3-diolefines with ziegler-type catalysts. J Polym Sci Part A Polym Chem 38:45–50

    Google Scholar 

  91. Topham P, Howse J, Fernyhough C, Ryan A (2007) The performance of poly(styrene)-block-poly(2-vinyl pyridine)-blockpoly(styrene) triblock copolymers as pH-driven actuators. Soft Matter 3:1506–1512

    Article  CAS  Google Scholar 

  92. Fragouli P, Iatrou H, Hadjichristidis N (2002) Synthesis and characterization of linear diblock and triblock copolymers of 2-vinyl pyridine and ethylene oxide. Polymer 43:7141–7144

    Article  CAS  Google Scholar 

  93. Han S, Lee D, Kim J (2007) Phase behavior of poly(2-vinylpyridine)-block-poly(4-vinylpyridine) copolymers. Macromolecules 40:7416–7419

    Article  CAS  Google Scholar 

  94. Hückstädt H, Göpfert A, Abetz V (2000) Influence of the block sequence on the morphological behavior of ABC triblock copolymers. Polymer 41:9089–9094

    Article  Google Scholar 

  95. du Sart G, Vukovic I, van Ekenstein G, Polushkin E, Loos K, ten Brinke G (2010) Self-assembly of supramolecular triblock copolymer complexes. Macromolecules 43:2970–2980

    Article  CAS  Google Scholar 

  96. Li H-J, Tsiang C-C R (2000) Preparation and characterization of a linear poly(4-vinyl pyridine)-b-polybutadiene-b-poly(4-vinylpyridine) using a t-butyllithium/m-diisopropenylbenzene diadduct as a dicarbanion initiator. Polymer 41:5601–5610

    Article  CAS  Google Scholar 

  97. Lee Y-H, Chang C-J, Kao C-J, Dai C-A (2010) In-situ template synthesis of a polymer/semiconductor nanohybrid using amphiphilic conducting block copolymers. Langmuir 26:4196–4206

    Article  CAS  Google Scholar 

  98. Kang N-G, Changez M, Lee J-S (2007) Living anionic polymerization of the amphiphilic monomer2-(4-vinylphenyl)pyridine. Macromolecules 40:8553–8559

    Article  CAS  Google Scholar 

  99. Hirao A, Kitamura K, Takenaka K, Nakahama S (1993) Protection and polymerization of functional monomers. 18. Syntheses of well-defined poly(vinylphenol), poly[(vinylphenyl)methanol], and poly[2-vinylphenyl)ethanol] by means of anionic living polymerization of styrene derivatives containing tert-butyldimethylsilyl ethers. Macromolecules 26:4995–5003

    Article  CAS  Google Scholar 

  100. Baranauskas V III, Zalich M, Saunders M, St. Pierre T, Riffle J (2005) Poly(styrene-b-4-vinylphenoxyphthalonitrile)-cobalt complexes and their conversion to oxidatively stable cobalt nanoparticles. Chem Mater 17:5246–5254

    Article  CAS  Google Scholar 

  101. Natalello A, Tonhauser C, Frey H (2013) Anionic polymerization of para-(1-ethoxy ethoxy)styrene: rapid access to poly(p-hydroxystyrene) copolymer architectures. ACS Macro Lett 2:409–413

    Article  CAS  Google Scholar 

  102. Vila-Ortega A, Vázquez-Torres H (2007) Living anionic polymerization of 2-vinyldibenzothiophene: homopolymer and block copolymers with styrene. J Polym Sci Part A Polym Chem 45:1993–2003

    Article  CAS  Google Scholar 

  103. (a) Natori I, Natori S, Usui H, Sato H (2008) Anionic polymerization of 4-diphenylaminostyrene: characteristics of the alkyllithium/N,N,N’,N’-tetramethylethylenediamine system for living anionic polymerization. Macromolecules 41:3852–3858; (b) Natori I, Natori S, Sekikawa H, Takahashi T, Ogino K, Tsuchiya K, Sato H (2010) Poly(4-diphenylaminostyrene) with a well-defined polymer chain structure: controllable optical and electrical properties. Polymer 51:1501–1506

    Google Scholar 

  104. Natori I, Natori S, Sekikawa H, Takahashi T, Sato H (2010) Synthesis and characterization of poly(4-diphenylaminostyrene)-poly(9-vinylanthracene) binary block copolymer. J App Polym Sci 118:69–73

    Article  CAS  Google Scholar 

  105. Higashihara T, Ueda M (2009) Living anionic polymerization of 4-vinyltriphenylamine for synthesis of novel block copolymers containing low-polydisperse poly(4-vinyltriphenylamine) and regioregular poly(3-hexylthiophene) segments. Macromolecules 42:8794–8800

    Article  CAS  Google Scholar 

  106. (a) Lafitte B, Jannasch P (2007) Chapter three on the prospects for phosphonated polymers as proton-exchange fuel cell membranes. Adv Fuel Cells 1:119–185; (b) Rusanov A, Kostoglodov P, Abadie M, Voytekunas V, Likhachev D (2008) Proton-conducting polymers at membranes carrying phosphonic acid groups. Adv Polym Sci 216:125–155

    Google Scholar 

  107. Perrin R, Elomaa M, Jannasch P (2009) Nanostructured proton conducting polystyrene-poly(vinylphosphonic acid) block copolymers prepared via sequential anionic polymerizations. Macromolecules 42:5146–5154

    Article  CAS  Google Scholar 

  108. Wagner T, Manhart A, Deniz N, Kaltbeitzel A, Wagner M, Brunklaus G, Meyer W (2009) Vinylphosphonic acid homo- and block copolymers. Macromol Chem Phys 210:1903–1914

    Article  CAS  Google Scholar 

  109. Kosaka Y, Kitazawa K, Inomata S, Ishizone T (2013) Living anionic polymerization of benzofulvene: highly reactive fixed transoid 1,3-diene. ACS Macro Lett 2:164–167

    Article  CAS  Google Scholar 

  110. de Paz Báñez MV, Robinson KL, Armes SP (2000) Synthesis and solution properties of dimethylsiloxane−2-(dimethylamino)ethyl methacrylate block copolymers. Macromolecules 33:451–456

    Article  CAS  Google Scholar 

  111. Lee J, Hogen-Esch TE (2001) Synthesis and characterization of narrow molecular weight distribution AB and ABA poly(vinylpyridine)−poly(dimethylsiloxane) block copolymers via anionic polymerization. Macromolecules 34:2805–2811

    Article  CAS  Google Scholar 

  112. Bellas V, Iatrou H, Hadjichristidis N (2000) Controlled anionic polymerization of hexamethylcyclotrisiloxane. Model linear and miktoarm star co- and terpolymers of dimethylsiloxane with styrene and isoprene. Macromolecules 33:6993–6997

    Article  CAS  Google Scholar 

  113. Cai GP, Weber WP (2004) Synthesis of terminal Si–H irregular tetra-branched star polysiloxanes. Pt-catalyzed hydrosilylation with unsaturated epoxides. Polysiloxane films by photo-acid catalyzed crosslinking. Polymer 45:2941–2948

    Article  CAS  Google Scholar 

  114. Boehm P, Mondeshki M, Frey H (2012) Polysiloxane-backbone block copolymers in a one-pot synthesis: a silicone platform for facile functionalization. Macromol Rapid Commun 33:1861–1867

    Article  CAS  Google Scholar 

  115. Davis S (1997) Biomedical applications of nanotechnology – implications for drug targeting and gene therapy. Trends Biotechnol 15:217–224

    Article  CAS  Google Scholar 

  116. Quirk RP, Ma J-J (1988) Characterization of the functionalization reaction product of poly(styryl)lithium with ethylene oxide. J Polym Sci Polym Chem Ed 26:2031–2037

    Article  CAS  Google Scholar 

  117. (a) Ekizoglou N, Hadjichristidis N (2001) Benzyl potassium: an efficient one-pot initiator for the synthesis of block co- and terpolymers of ethylenoxide. J Polym Sci Polym Chem Ed 39:1198–1201; (b) Ekizoglou N, Hadjichristidis N (2002) Synthesis of model linear tetrablock quaterpolymers and pentablock quintopolymers of ethylene oxide. J Polym Sci Polym Chem Ed 40:2166–2170

    Google Scholar 

  118. Boschet F, Branger C, Margaillan A, Hogen-Esch T (2005) Associative properties of perfluorooctyl end-functionalized polystyrene–poly(ethyleneoxide) diblock copolymers. Polym Int 54:90–95

    Article  CAS  Google Scholar 

  119. Chen J, Frisbie D, Bates F (2009) Lithium perchlorate-doped poly(styrene-b-ethylene oxide-b-styrene) lamellae-forming triblock copolymer as high capacitance, smooth, thin film dielectric. J Phys Chem C 113:3903–3908

    Article  CAS  Google Scholar 

  120. Bailey T, Pham H, Bates F (2001) Morphological behavior bridging the symmetric AB and ABC states in the poly(styrene-b-isoprene-b-ethylene oxide) triblock copolymer system. Macromolecules 34:6994–7008

    Article  CAS  Google Scholar 

  121. Meuler A, Ellison C, Qin J, Evans C, Hillmyer M, Bates F (2009) Polydispersity effects in poly(isoprene-b-styrene-b-ethylene oxide) triblock terpolymers. J Chem Phys 130:234903

    Article  CAS  Google Scholar 

  122. (a) Brannan A, Bates F (2004) ABCA tetrablock copolymer vesicles. Macromolecules 37:8816–8819; (b) Hillmyer M, Bates F (1996) Synthesis and characterization of model polyalkane−poly(ethylene oxide) block copolymers. Macromolecules 29:6994–7002

    Google Scholar 

  123. Touris A, Lee S, Hillmyer M, Bates F (2012) Synthesis of tri- and multiblock polymers with asymmetric poly(ethylene oxide) end blocks. ACS Macro Lett 1:768–771

    Article  CAS  Google Scholar 

  124. Seow PK, Gallot Y, Skoulios A (1975) Synthèse et caractérisation de copolymères séquencés poly(méthacrylate d’alkyle)/poly(oxyéthylène). Makromol Chem 176:3153–3166

    Article  CAS  Google Scholar 

  125. Suzuki T, Murakami Y, Takegami Y (1980) Synthesis and characterization of block copolymers of poly(ethylene oxide) and poly(methyl methacrylate). Polym J 12:183–192

    Article  CAS  Google Scholar 

  126. Garg D, Horing S, Ulbricht J (1984) Initiation of anionic polymerization of methyl methacrylate by living poly(ethylene oxide) anions, a new way for the synthesis of poly(ethylene oxide)-b-poly(methyl methacrylate). Macromol Chem Rapid Commun 5:615–618

    Article  CAS  Google Scholar 

  127. Reuter H, Berlinova I, Höring S, Ulbricht J (1991) The anionic block copolymerization of ethylene oxide with tert-butyl methacrylate. Diblock and multiblock copolymers. Eur Polym J 27:673–680

    Article  CAS  Google Scholar 

  128. Dhara M, Baskaran D, Sivram S (2008) Synthesis of amphiphilic poly(methyl methacrylateb-ethylene oxide) copolymers from monohydroxy telechelic poly(methyl methacrylate) as macroinitiator. J Polym Sci Part A Polym Chem 46:2132–2144

    Article  CAS  Google Scholar 

  129. Mountrichas G, Pispas S (2007) Novel double hydrophilic block copolymers based on poly(p-hydroxystyrene) derivatives and poly(ethylene oxide). J Polym Sci Part A Polym Chem 45:5790–5799

    Article  CAS  Google Scholar 

  130. Mountrichas G, Mantzaridis C, Pispas S (2006) Well-defined flexible polyelectrolytes with two cationic sites per monomeric unit. Macromol Rapid Commun 27:289–294

    Article  CAS  Google Scholar 

  131. Gohy J-F, Willet N, Varshney S, Zhang J-X, Jerôme R (2001) Core–shell–corona micelles with a responsive shell. Angew Chem Int Ed 40:3214–3216

    Article  CAS  Google Scholar 

  132. Schmalz H, Knoll A, Müller AJ, Abetz V (2002) Synthesis and characterization of ABC triblock copolymers with two different crystalline end blocks: influence of confinement on crystallization behavior and morphology. Macromolecules 35:10004–10013

    Article  CAS  Google Scholar 

  133. (a)Taribagil R, Hillmyer M, Lodge T (2010) Hydrogels from ABA and ABC triblock polymers. Macromolecules 43:5396–5404; (b) Hillmyer M, Bates F (1996) Synthesis and characterization of model polyalkane−poly(ethylene oxide) block copolymers. Macromolecules 29:6994–7002

    Google Scholar 

  134. (a) Larras V, Bru N, Breton P, Riess G (2000) Synthesis and micellization of amphiphilic poly(ethylene oxide)-block-poly(methylidene malonate 2.1.2) diblock copolymers. Macromol Rapid Commun 21:1089–1092; (b) Bru-Magniez N, Larras V, Riess G, Breton P, Couvreur P, Roques Carmes C (1998) Novel surfactant copolymers based on methylidene malonate. WO 99/38898 (1999)/FR19980001001(1998)

    Google Scholar 

  135. Studer P, Larras V, Riess G (2008) Amino end-functionalized poly(ethylene oxide)-block-poly(methylidene malonate 2.1.2) block copolymers: synthesis, characterization, and chemical modification for targeting purposes. Eur Polym J 44:1714–1721

    Article  CAS  Google Scholar 

  136. Jerome C, Lecomte P (2008) Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization. Adv Drug Deliv Rev 60:1056–1076

    Article  CAS  Google Scholar 

  137. Van Butsele K, Cajot S, Van Vlierberghe S, Dubruel P, Passirani C, Benoit J-P, Jérôme R, Jérôme C (2009) pH-responsive flower-type micelles formed by a biotinylated poly(2-vinylpyridine)-block-poly(ethylene oxide)-block-poly(e-caprolactone) triblock copolymer. Adv Funct Mater 19:1416–1425

    Article  CAS  Google Scholar 

  138. Ogle C, Strickler F, Gordon G (1993) Reaction of polystyryllithium with tetrahydrofuran. Macromolecules 26:5803–5805

    Article  CAS  Google Scholar 

  139. (a) Dimitrov P, Rangelov S, Dworak A, Haraguchi N, Hirao A, Tsvetanov C (2004) Triblock and radial star-block copolymers comprised of poly(ethoxyethyl glycidyl ether), polyglycidol, poly(propylene oxide) and polystyrene obtained by anionic polymerization initiated by Cs initiators. Macromol Symp 215:127–139; (b) Dworak A, Baran G, Trzebicka B, Walach W (1999) Polyglycidol-block-poly(ethylene oxide)-block-polyglycidol: synthesis and swelling properties. React Funct Polym 42:31–36; (c) Lapienis G, Penczek S (2005) One-pot synthesis of star-shaped macromolecules containing polyglycidol and poly(ethylene oxide) arms. Biomacromolecules 6:752–762; (d) Kaluzynski K, Pretula J, Lapienis G, Basko M, Bartczak Z, Dworak A, Penczek S (2001) Dihydrophilic block copolymers with ionic and nonionic blocks. I. Poly(ethylene oxide)-b-polyglycidol with OP(O)(OH)2, COOH, or SO3H functions: synthesis and influence for CaCO3 crystallization. J Polym Sci Part A Polym Chem 39:955–963; (e) Mendrek A, Mendrek S, Trzebicka B, Kuckling D, Walach W, Adler HJ, Dworak A (2005) Polyether core-shell cylinder–polymerization of polyglycidol macromonomers. Macromol Chem Phys 206:2018–2026; (f) Walach W, Kowalczuk A, Trzebicka B, Dworak A (2001) Synthesis of high-molar mass arborescent-branched polyglycidol via sequential grafting. Macromol Rapid Commun 22:1272–1277

    Google Scholar 

  140. (a) Hsieh H, Quirk RP (1996) Anionic polymerizations principles and practical applications. Marcel Dekker, New York, p 688; (b) Wesdemiotis C, Arnould MA, Lee Y, Quirk RP (2000) MALDI TOF mass spectrometry of the products from novel anionic polymerizations. Polym Prepr 41(1):629–630

    Google Scholar 

  141. Dimitrov P, Utrata-Wesołek A, Rangelov S, Wałach W, Trzebicka B, Dworak A (2006) Synthesis and self-association in aqueous media of poly(ethylene oxide)/poly(ethyl glycidyl carbamate) amphiphilic block copolymers. Polymer 47:4905–4915

    Article  CAS  Google Scholar 

  142. Ah Toy A, Reinicke S, Müller A, Schmalz H (2007) One-pot synthesis of polyglycidol-containing block copolymers with alkyllithium initiators using the phosphazene base t-BuP4. Macromolecules 40:5241–5244

    Article  CAS  Google Scholar 

  143. Taton D, Le Borgne A, Sepulchre M, Spassky N (1994) Synthesis of chiral and racemic functional polymers from glycidol and thioglycidol. Macromol Chem Phys 195:139–148

    Article  CAS  Google Scholar 

  144. (a) Muller M, Zentel R (1994) Photochemical amplification of chiral induction in polyisocyanates. Macromolecules 27:4404–4406; (b) Shibaev PV, Tang K, Genack AZ, Kopp V, Green MM (2002) Lasing from a stiff chain polymeric lyotropic cholesteric liquid crystal. Macromolecules 35:3022–3025; (c) Maeda K, Okamoto Y (1998) Synthesis and conformation of optically active poly(phenyl isocyanate)s bearing an ((S)-(α-methylbenzyl)carbamoyl) group. Macromolecules 31:1046–1052

    Google Scholar 

  145. Bur AJ, Fetters LJ (1976) The chain structure, polymerization, and conformation of polyisocyanates. Chem Rev 76:727–746

    Article  CAS  Google Scholar 

  146. (a) Lee JS, Ryu SW (1999) Anionic living polymerization of 3-(triethoxysilyl)propyl isocyanate. Macromolecules 32:2085–2087; (b) Shin YD, Kim SY, Ahn JH, Lee JS (2001) Synthesis of poly(n-hexyl isocyanate) by controlled anionic polymerization in the presence of NaBPh4. Macromolecules 34:2408–2410

    Google Scholar 

  147. (a) Ahn JH, Shin YD, Kim SY, Lee JS (2003) Synthesis of well-defined block copolymers of n-hexyl isocyanate with isoprene by living anionic polymerization. Polymer 44:3847–3854; (b) Ahn JH, Lee CH, Shin YD, Lee JS (2004) Generation of highly stable amidate anion in anionic polymerization of 3-(triethylsilyl)propyl isocyanate. J Polym Sci Part A Polym Chem 42:933–940

    Google Scholar 

  148. Vazaios A, Pitsikalis M, Hadjichristidis N (2003) Triblock copolymers and pentablock terpolymers of n-hexyl isocyanate with styrene and isoprene: synthesis, characterization and thermal properties. J Polym Sci Polym Chem Ed 41:3094–3102

    Article  CAS  Google Scholar 

  149. Zorba G, Vazaios A, Pitsikalis M, Hadjichristidis N (2005) Anionic polymerization of n-hexyl isocyanate with monofunctional initiators. Application in the synthesis of diblock copolymers with styrene and isoprene. J Polym Sci Polym Chem Ed 43:3533–3542

    Article  CAS  Google Scholar 

  150. Shin Y-D, Han S-H, Samal S, Lee J-S (2005) Synthesis of poly(2-vinyl pyridine)-b-poly (n-hexylisocyanate) amphiphilic coil-rod block copolymer by anionic polymerization. J Polym Sci Part A Polym Chem 43:607–615

    Article  CAS  Google Scholar 

  151. Rahman M, Samal S, Lee J-S (2007) Quantitative in situ coupling of living diblock copolymers for the preparation of amphiphilic coil-rod-coil triblock copolymer poly(2-vinylpyridine)-b-poly(n-hexylisocyanate)-b-poly(2-vinylpyridine). Macromolecules 40:9279–9283

    Article  CAS  Google Scholar 

  152. Ahn J-H, Shin Y-D, Nath G, Park S-Y, Rahman M, Samal S, Lee J-S (2005) Unprecedented control over polymerization of n-hexyl isocyanate using an anionic initiator having synchronized function of chain-end protection. J Am Chem Soc 127:4132–4133

    Article  CAS  Google Scholar 

  153. Min J, Yoo H-S, Shah P, Chae C-G, Lee J-S (2013) Enolate anionic initiator, sodium deoxybenzoin, for leading living natures by formation of aggregators at the growth chain ends. J Polym Sci Part A Polym Chem 51:1742–1748

    Article  CAS  Google Scholar 

  154. Wurm F, Hilf S, Frey H (2009) Electroactive linear–hyperbranched block copolymers based on linear poly(ferrocenylsilane)s and hyperbranched poly(carbosilane)s. Chem Eur J 15:09068–09077

    Article  CAS  Google Scholar 

  155. Ma Y, Dong W-F, Hempenius MA, Möhwald H, JuliusVancso G (2006) Redox-controlled molecular permeability of composite-wall microcapsules. Nat Mater 5:724–729

    Article  CAS  Google Scholar 

  156. Ieong NS, Manners I (2009) Anionic ring-opening polymerization of a germanium-bridged [1]ferrocenophane: synthesis and morphology of well-defined polyferrocenylgermane homopolymers and block copolymers. Macromol Chem Phys 210:1080–1086

    Article  CAS  Google Scholar 

  157. Patra SK, Whittell GR, Nagiah S, Ho C-L, Wong W-Y, Manners I (2010) Photocontrolled living anionic polymerization of phosphorus-bridged [1]ferrocenophanes: a route to well-defined polyferrocenylphosphine (PFP) homopolymers and block copolymers. Chem Eur J 16:3240–3250

    Article  CAS  Google Scholar 

  158. Goseki R, Hirai T, Kakimoto M, Hayakawa T (2012) Iron oxide arrays prepared from ferrocene- and silsesquioxane-containing block copolymers. Int J Polym Sci 2012:1–10

    Article  CAS  Google Scholar 

  159. Bellas V, Rehahn M (2009) Block copolymer synthesis via chemoselective stepwise coupling reactions. Macromol Chem Phys 210:320–330

    Article  CAS  Google Scholar 

  160. (a) Wang XS, Winnik MA, Manners I (2002) Synthesis and aqueous self-assembly of a polyferrocenylsilane-block-poly(aminoalkyl methacrylate) diblock copolymer. Macromol Rapid Commun 23:210–213; (b) Lee J, Hogen-Esch TE (2001) Synthesis and characterization of narrow molecular weight distribution AB and ABA poly(vinylpyridine)−poly(dimethylsiloxane) block copolymers via anionic polymerization. Macromolecules 34:2805–2811

    Google Scholar 

  161. (a) Mahajan S, Cho B, Allgaiger J, Fetters LJ, Coates GW, Wiesner U (2004) Synthesis of amphiphilic ABC triblock copolymers with PEO as the middle block. Macromol Rapid Commun 25:1889–1894; (b) Zhang K, Ye Z, Subramanian R (2008) Synthesis of block copolymers of ethylene with styrene and n-butyl acrylate via a tandem strategy combining ethylene “living” polymerization catalyzed by a functionalized Pd−diimine catalyst with atom transfer radical polymerization. Macromolecules 41:640–649

    Google Scholar 

  162. (a) Quémener D, Davis TP, Barner-Kowollik C, Stenzel MH (2006) RAFT and click chemistry: a versatile approach to well-defined block copolymers. Chem Commun 5051–5053; (b) Durmaz H, Dag A, Altintas O, Erdogan T, Hizal G, Tunca U (2007) One-pot synthesis of ABC type triblock copolymers via in situ click [3 + 2] and Diels−Alder [4 + 2] reactions. Macromolecules 40:191–198; (c) Opsteen JA, van Hest JCM (2007) Modular synthesis of ABC type block copolymers by “click” chemistry. J Polym Sci Part A Polym Chem 45:2913–2924; (d) Sinnwell S, Inglis AJ, Davis TP, Barner-Kowollik C, Stenzel MH (2008) An atom-efficient conjugation approach to well-defined block copolymers using RAFT chemistry and hetero Diels–Alder cycloaddition. Chem Commun 17:2052–2054

    Google Scholar 

  163. Natalello A, Alkan A, Friedel A, Lieberwirth I, Frey H, Wurm FR (2013) Enlarging the toolbox: epoxide termination of polyferrocenylsilane (PFS) as a key step for the synthesis of amphiphilic PFS−polyether block copolymers. ACS Macro Lett 2:313–316

    Article  CAS  Google Scholar 

  164. Vanderark L, Januszewski E, Gwyther J, Manners I (2011) Studies of the end-capping of living anionic poly(ferrocenyldimethylsilane) with 1,1-diphenylethylene. Eur Polym J 47:823–826

    Article  CAS  Google Scholar 

  165. Wang H, Winnik MA, Manners I (2007) Synthesis and self-assembly of poly(ferrocenyldimethylsilane-b-2-vinylpyridine) diblock copolymers. Macromolecules 40:3784–3789

    Article  CAS  Google Scholar 

  166. (a) Kloninger C, Rehahn M (2004) 1,1-dimethylsilacyclobutane-mediated living anionic block copolymerization of [1]dimethylsilaferrocenophane and methyl methacrylate. Macromolecules 37:1720–1727; (b) Kloninger C, Rehahn M (2007) Styrene–ferrocenyldimethylsilane–methyl methacrylate triblock copolymers: synthesis and phase morphology. Macromol Chem Phys 208:833–4

    Google Scholar 

  167. Smith GS, Patra SK, Vanderark L, Saithong S, Charmant JPH, Manners I (2010) Photocontrolled living anionic polymerization of silicon-bridged [1]ferrocenophanes with fluorinated substituents: synthesis and characterization of fluorinated polyferrocenylsilane (PFS) homopolymers and block copolymers. Macromol Chem Phys 211:303–312

    Article  CAS  Google Scholar 

  168. Mizuta T, Onishi M, Miyoshi K (2000) Photolytic ring-opening polymerization of phosphorus-bridged [1]ferrocenophane coordinating to an organometallic fragment. Organometallics 19:5005–5009

    Article  CAS  Google Scholar 

  169. (a) Tanabe M, Manners I (2004) Photolytic living anionic ring-opening polymerization (ROP) of silicon-bridged [1]ferrocenophanes via an iron-cyclopentadienyl bond cleavage mechanism. J Am Chem Soc 126:11434–11435; (b) Tanabe M, Vandermeulen GWM, Chan WY, Cyr PW, Vanderark L, Rider DA, Manners I (2006) Photocontrolled living polymerizations. Nat Mater 5:467–470

    Google Scholar 

  170. (a) Cheng JY, Ross CA, Chan VZH, Thomas EL, Lammertink RGH, Vancso GJ (2001) Formation of a cobalt magnetic dot array via block copolymer lithography. Adv Mater 13:1174–1178; (b) Lu J, Chamberlin D, Rider DA, Liu MJ, Manners I, Russell TP (2006) Using a ferrocenylsilane-based block copolymer as a template to produce nanotextured Ag surfaces: uniformly enhanced surface enhanced Raman scattering active substrates. Nanotechnology 17:5792–5797; (c) Lammertink RGH, Hempenius MA, Chan VZH, Thomas EL, Vancso GJ (2001) Poly(ferrocenyldimethylsilanes) for reactive ion etch barrier applications. Chem Mater 13:429–434; (e) Chuang VP, Ross CA, Gwyther J, Manners I (2009) Self-assembled nanoscale ring arrays from a polystyrene-b-polyferrocenylsilane-b-poly(2-vinylpyridine)triblock terpolymer thin film. Adv Mater 21:3789–3793; (f) Chuang VP, Gwyther J, Mickiewicz RA, Manners I, Ross CA (2009) Templated self-assembly of square symmetry arrays from an ABC triblock terpolymer. Nano Lett 9:4364–4369

    Google Scholar 

  171. (a) Espada L, Robillard J, Shadaram M, Pannell KH (2000) Ferrocenylenesilylene polymers as coatings for tapered optical-fiber gas sensors. J Inorg Organomet Polym 10:169–176; (b) Paquet C, Cyr PW, Kumacheva E, Manners I (2004) Rationalized approach to molecular tailoring of polymetallocenes with predictable optical properties. Chem Mater 16:5205–5211

    Google Scholar 

  172. (a) Eitouni HB, Balsara NP (2004) Effect of chemical oxidation on the self-assembly of organometallic block copolymers. J Am Chem Soc 126:7446–7447; (b) Arsenault AC, Puzzo DP, Manners I, Ozin GA (2007) Photonic-crystal full-colour displays. Nature Photonics 1:468–472

    Google Scholar 

  173. Sun Q, Lam JWY, Xu K, Xu H, Cha JAP, Wong PCL, Wen G, Zhang X, Jing X, Wang F, Tang BZ (2000) Nanocluster-containing mesoporous magnetoceramics from hyperbranched organometallic polymer precursors. Chem Mater 12:2617–2624

    Google Scholar 

  174. Hinderling C, Keles Y, Stoeckli T, Knapp HF, De Los Acros T, Oelhafen P, Korezagin I, Hempenius MA, Vancso GJ, Pugin R, Heinzelmann H (2004) Organometallic block copolymers as catalyst precursors for templated carbon nanotube growth. Adv Mater 16:876–879

    Article  CAS  Google Scholar 

  175. (a) Rider DA, Manners I (2007) Synthesis, self‐assembly, and applications of polyferrocenylsilane block copolymers. Polymer Rev 47:165–195; (b) Manners I (1999) Poly(ferrocenylsilanes): novel organometallic plastics. Chem Commun 10:857–865

    Google Scholar 

  176. (a) Loo YL, Register RA, Ryan AJ (2002) Modes of crystallization in block copolymer microdomains: breakout, templated, and confined. Macromolecules 35:2365–2374; (b) Zhu L, Cheng SZD, Calhoun BH, Ge Q, Quirk RP, Thomas EL (2000) Crystallization temperature-dependent crystal orientations within nanoscale confined lamellae of a self-assembled crystalline−amorphous diblock copolymer. J Am Chem Soc 122:5957–5967; (c) Li LB, Serero Y, Koch MHJ, de Jeu WH (2003) Microphase separation and crystallization in an asymmetric diblock copolymer: Coupling and competition. Macromolecules 36:529–532; (d) Huang P, Zhu L, Cheng SZD, Ge Q, Quirk RP, Thomas EL (2001) Crystal orientation changes in two-dimensionally confined nanocylinders in a poly(ethylene oxide)-b-polystyrene/polystyrene blend macromolecules 34:6649–6657; (e) Chen HL, Hsiao SC, Lin TL, Yamauchi K, Hasegawa H, Hashimoto T (2001) Microdomain-tailored crystallization kinetics of block copolymers. Macromolecules 34:671–674

    Google Scholar 

  177. (a) Rider DA, Cavicchi KA, Power-Billard KN, Russell TP, Manners I (2005) Diblock copolymers with amorphous atactic polyferrocenylsilane blocks: synthesis, characterization, and self-assembly of polystyrene-block-poly(ferrocenylethylmethyl silane) in the bulk state. Macromolecules 38:6931–6938; (b) Eloi JC, Rider DA, Wang JY, Russell TP, Manners I (2008) Amorphous diblock copolymers with a high organometallic block volume fraction: synthesis, characterization and self-assembly of polystyrene-block-poly(ferrocenylethylmethylsilane) in the bulk state. Macromolecules 41:9474–9479; (c) Roerdink M, Hempenius MA, Vancso GJ (2005) Large area ordering at room temperature in thin films of poly(isoprene-block-ferrocenylsilane)s for nanofabrication. Chem Mater 17:1275–1278

    Google Scholar 

  178. Gwyther J, Ian Manners I (2009) Diblock copolymers with an amorphous, high glass transition temperature, organometallic block: synthesis, characterisation and self-assembly of polystyrene-b-poly(ferrocenylisopropylmethylsilane) in the bulk state. Polymer 50:5384–5389

    Article  CAS  Google Scholar 

  179. Resendes R, Massey J, Dorn H, Winnik MA, Manners I (2000) A convenient, transition metal-catalyzed route to water-soluble amphiphilic organometallic block copolymers: synthesis and aqueous self-assembly of poly(ethylene oxide)-block-poly(ferrocenylsilane). Macromolecules 33:8–10

    Article  CAS  Google Scholar 

  180. Zhang M, Rupar PA, Feng C, Lin K, Lunn DJ, Oliver A, Nunns A, Whittell GR, Manners I, Winnik MA (2013) Modular synthesis of polyferrocenylsilane block copolymers by Cu-catalyzed alkyne/azide “click” reactions. Macromolecules 46:1296–1304

    Article  CAS  Google Scholar 

  181. Gohy J-F, Lohmeijer BGG, Alexeev A, Wang X-S, Manners I, Winnik MA, Schubert US (2004) Cylindrical micelles from the aqueous self-assembly of an amphiphilic poly(ethylene oxide)–b-poly(ferrocenylsilane) (PEO-b-PFS) block copolymer with a metallo-supramolecular linker at the block junction. Chem Eur J 10:4315–4323

    Article  CAS  Google Scholar 

  182. (a) Kloninger C, Rehahn M (2004) 1,1-dimethylsilacyclobutane-mediated living anionic block copolymerization of [1]dimethylsilaferrocenophane and methyl methacrylate. Macromolecules 37:1720–1727; (b) Kloninger C, Knecht D, Rehahn M (2004) Microphase behaviour of ferrocenyldimethylsilane-b-methylmethacrylate diblock copolymers. Polymer 45:8323–8332

    Google Scholar 

  183. (a) Quirk RP, Corona-Galvan S (2001) Controlled anionic synthesis of polyisoprene−poly(2-vinylpyridine) diblock copolymers in hydrocarbon solution. Macromolecules 34:1192–1197; (b) Clegg W, Dunbar L, Horsburgh L, Mulvey RE (1996) Stoichiometric dependence of the long-established reaction of butyllithium with pyridine: a hidden secondary reaction that produces a pyridine adduct of a lithiodihydropyridine. Angew Chem Int Ed 35:753–755

    Google Scholar 

  184. Wang X, Winnik MA, Manners I (2005) Synthesis and self-assembly of poly(ferrocenyldimethylsilane-b-dimethylaminoethyl methacrylate): toward water-soluble cylinders with an organometallic core. Macromolecules 38:1928–1935

    Article  CAS  Google Scholar 

  185. Eloi J-C, Rider DA, Wang J-Y, Russell TP, Manners I (2008) Amorphous diblock copolymers with a high organometallic block volume fraction: synthesis, characterization and self-assembly of polystyrene-block-poly(ferrocenylethylmethylsilane) in the bulk state. Macromolecules 41:9474–9479

    Article  CAS  Google Scholar 

  186. Rider DA, Cavicchi KA, Power-Billard KN, Russell TP, Manners I (2005) Diblock copolymers with amorphous atactic polyferrocenylsilane blocks: synthesis, characterization, and self-assembly of polystyrene-block-poly(ferrocenylethylmethyl silane) in the bulk state. Macromolecules 38:6931–6938

    Article  CAS  Google Scholar 

  187. (a) Mark JE, Allcock HR, West R (2005) Inorganic polymers, 2nd edn. Oxford University Press, New York; (b) Baumgartner T, Reau R (2006) Organophosphorus π-conjugated materials. Chem Rev 106:4681–4727; (c) Noonan KJT, Gates DP (2007) Inorganic and organometallic polymers. Annu Rep Prog Chem 103:407–427; (d) Tsang CW, Baharloo B, Riendel D, Yam M, Gates DP (2004) Radical copolymerization of a phosphaalkene with styrene: new phosphine-containing macromolecules and their use in polymer-supported catalysis. Angew Chem Int Ed 43:5682–5685; (e) Huynh K, Lough AJ, Manners I (2006) Reactions of P-donor ligands with N-silyl(halogeno)organophosphoranimines: formation of cations with P−P coordination bonds and poly(alkyl/aryl)phosphazenes at ambient temperature. J Am Chem Soc 128:14002–14003; (f) Raab M, Schick G, Fondermann R, Dolg M, Henze W, Weynand U, Gschwind RM, Fischer K, Schimdt M, Niecke E (2006) A pH-functionalized polyphosphazene: a macromolecule with a highly flexible backbone. Angew Chem Int Ed 45:3083–3086; (g) Su HC, Fadhel O, Yang CJ, Cho TY, Fave C, Hissler M, Wu CC, Réau R (2006) Toward functional π-conjugated organophosphorus materials: design of phosphole-based oligomers for electroluminescent devices. J Am Chem Soc 128:983–995; (h) Vanderark LA, Clark TJ, Rivard E, Manners I, Slootweg JC, Lammertsma K (2006) Anionic ring-opening polymerization of a strained phosphirene: a route to polyvinylenephosphines. Chem Commun 31:3332–3333; (i) Naka K, Umeyama T, Nakahashi A, Chujo Y (2007) Synthesis of poly(vinylene−phosphine)s: ring-collapsed radical alternating copolymerization of methyl-substituted cyclooligophosphine with acetylenic compounds. Macromolecules 40:4854–4858; (j) Noonan KJT, Gillon BH, Cappello V, Gates DP (2008) Phosphorus-containing block copolymer templates can control the size and shape of gold nanostructures. J Am Chem Soc 130:12876–12877; (k) Gillon BH, Patrick BO, Gates DP (2008) Macromolecular complexation of poly(methylenephosphine) to gold(I): a facile route to highly metallated polymers. Chem Commun 18:2161–2163

    Google Scholar 

  188. Stoeckli-Evans H, Osborne AG, Whiteley RH (1980) Ring-tilted ferrocenophanes. the crystal and molecular structures of (1,1’-ferrocenediyl)diphenylgermane and (1,1’-ferrocenediyl)phenylphosphine. J Organomet Chem 194:91–101

    Article  CAS  Google Scholar 

  189. (a) Foucher DA, Edwards M, Burrow RA, Lough AJ, Manners I (1994) Ring-opening polymerization of strained, ring-tilted [1]ferrocenophanes with germanium in the bridge: structures of the [1]germaferrocenophane Fe(η5-C5H4)2GeMe2 and the ferrocenylgermane Fe(η5-C5H4GeEt2Cl) (η5-C5H5) organometallics 13:4959–4966; (b) Zürcher S, Gramlich V, Togni A (1999) Germanium-containing ferrocenes and ferrocenophanes. Potential precursors for ring-opening polymerizations and ‘germaferrocenes’. Inorg Chim Acta 291:355–364; (c) MacLachlan MJ, Lough AJ, Geiger WE, Manners I (1998) Synthesis, structures, and properties of strained spirocyclic [1]sila- and [1]germaferrocenophanes and tetraferrocenylsilane. Organometallics 17:1873–1883

    Google Scholar 

  190. Gallei M, Schmidt BVKJ, Klein R, Rehahn M (2009) Defined poly[styrene-block-(ferrocenylmethylmethacrylate)] diblock copolymers via living anionic polymerization. Macromol Rapid Commun 30:1463–1469

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Athens, Panepistimiopolis Zografou, Athens, 15771, Greece

    Georgios Theodosopoulos & Marinos Pitsikalis

Authors
  1. Georgios Theodosopoulos
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Marinos Pitsikalis
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia

    Nikos Hadjichristidis

  2. Tokyo Institute of Technology, Tokyo, Japan

    Akira Hirao

Abbreviations

Abbreviations

2VDBT:

2-Vinyldibenzenthiophene

4VP:

4-Vinyl pyridine

AFM:

Atomic force microscopy

AGE:

Allyl glycidyl ether

a-PA:

a-Phenyl acrylate

Bd:

Butadiene

BDMrSPrLi:

(tert-Butyldimethylsilyloxy)-1-propyl lithium

BF:

Benzofulvene

CHD:

1,3-Cyclohexadiene

Cp:

Cyclopentadienyl

CzEMA:

2-(N-carbazoyl)ethyl methacrylate

D3 :

Hexamethylcyclotrisiloxane

D4v :

Tetramethyltetravinylcyclotetrasiloxane

DABCO:

1,4-Diazabicyclo[2,2,2]octane

DAS:

4-Diphenylaminostyrene

DBAG:

N,N-Dibenzyl amino glycidol

DEAAm:

N,N-Diethylacrylamide

DEVP:

Diethylvinyl phosphonate

DIVP:

Diisopropylvinyl phosphonate

DMAEMA:

Dimethylaminoethylmethacrylate

DMAEMA:

2-(Dimethylamino)ethyl methacrylate

DME:

Dimethoxyethane

DPE:

Diphenylethylene

ECA:

Ethylcyanoacrylate

EEGE:

Ethoxyethyl glycidyl ether

EO:

Ethylene oxide

EtHA:

2-Ethyhexyl acrylate

Fc:

Ferrocene

FDMG:

Ferrocenyldimethylgermane

FMA:

2-(N-Methylperfluorbutanesulfonamido)ethyl methacrylate

HIC:

Hexyl isocyanate

I:

Isoprene

IPP:

2-Isopropenylpyridine

LCST:

Lower critical solution temperature

LiEA:

Lithium enolate of acetaldehyde

MAHE:

trans-1-Methacryloyloxy-2,4-hexadiene

MAHFC:

Methacrylichexylferrocenes

MAPOSS:

3-(3,5,7,9,11,13,15-Heptaisobutyl-pentacyclo[9.5.13,9.15,15,17,13]octasiloxan −1-yl) propyl methacrylate

MBA:

3-Methacryloyloxy-1,1’-biadamantane

MEEOLi:

2-(2-Methoxyethoxy)ethoxide lithium

MMA:

Methyl methacrylate

MPEG:

Poly(ethylene glycol)monomethyl ether

n-BuLi:

n-Butyllithium

NMR:

Nuclear magnetic resonance

NPHSO:

3,5-Bis(dimethylaminomethylene)hydroxystyrene

OFPMA:

2,2,3,3,4,4,5,5-Octafluoropentylmethacrylate

P(ε-CL):

Poly(ε-caprolactone)

P2VP:

Poly(2-vinyl pyridine)

P4VP:

Poly(4-vinyl pyridine)

PAGE:

Poly(allyl glycidyl ether)

PaMeS:

Poly(a-methylstyrene)

PCHD:

Polycyclohexadiene

PCHD:

Poly(1,3-cyclohexadiene)

PCzEMA:

Poly[2-(N-carbazoyl)ethyl methacrylate]

PDAS:

Poly(diphenylaminostyrene)

PDEAAm:

Poly(N,N-diethylacrylamide)

PDEVP:

Poly(diethylvinyl phosphonate)

PDEVP:

Poly(diethylvinyl phosphonate)

PDIVP:

Poly(diisopropylvinyl phosphonate)

PDMAAm:

Poly(N,N-dimethylacrylamide)

PDMAEMA:

Poly[(dimethylamino)ethyl methacrylate]

PDMS:

Poly(dimethylsiloxane)

PE:

Polyethylene

PECA:

Poly(ethylcyanoacrylate)

PEG:

Poly(ethylene glycol)

PEO:

Poly(ethylene oxide)

PEP:

Poly(ethylene-alt-propylene)

PFDMG:

Polyferrocenyldimethylgermane

PFDMS:

Poly(ferrocenyldimethylsilane)

PFIC:

Poly(furfuryl isocyanate)

PFiPMS:

Polyferrocenylisopropylmethylsilane

PFMMA:

Polyferrocenylmethylmethacrylate

PFPs:

Phosphorus-bridged polyferrocenes

PFS:

Poly(ferrocenosilanes)

PG:

Polyglycidol

PHIC:

Poly(hexyl isocyanate)

PI:

Polyisoprene

PIsOA:

Poly(isooctyl acrylate)

PLA:

Poly(lactic acid)

PMBA:

Poly(3-Methacryloyloxy-1,1’-biadamantane)

PMM:

Poly(methylidene malonate)

PMMA:

Poly(methyl methacrylate)

PMVS:

Poly(methylvinyl siloxane)

PnBuA:

Poly(n-butyl acrylate)

PNHSO:

Poly[3,5-bis(dimethylaminomethylene)hydroxystyrene]

POFPMA:

Poly(2,2,3,3,4,4,5,5-octafluoropentylmethacrylate)

PpEES:

Poly[p(1-ethoxy ethoxy)styrene]

PPP:

Polyphenylene

PS:

Polystyrene

PtBOS:

Poly(4-tert-butoxystyrene)

PtBS:

Poly(tert-butoxystyrene)

PtBuA:

Poly(tert-butylacrylate)

PTESPI:

Poly[3-(triethylsilyl)propyl isocyanate]

PTFEMA:

Poly(2,2,2-trifluorethylmethacrylate)

PTMSS:

Poly(trimethylsilylstyrene)

PVAN:

Poly(vinylanthracene)

PVF:

Poly(vinylferrocene)

PVPh:

Poly(vinylphenol)

PVPPy:

Poly[2-(4-vinylphenyl)pyridine]

S:

Styrene

SAXS:

Small angle X-ray scattering

SEC:

Size exclusion chromatography

sec-BuLi:

sec-Butyllithium

SiOPLi:

3-tert-Butyldimethylsilyloxy-1-propyllithium

SMA:

Stearyl methacrylate

TBAF:

Tetrabutylammonium fluoride

tBuA:

tert-Butylacrylate

t-BuOK:

Potassium tert-butoxide

TEM:

Transmission Electron Microscopy

tert-BuLi :

tert-Butyllithium

Tg:

Glass transition temperature

THF:

Tetrahydrofuran

TIPSOPrLi:

3-Triisopropylsilyloxy-1-propyllithium

TMEDA:

Tetramethylethylenediamine

TMSS:

Trimethylsilylstyrene

TOQ:

Tertrachloror-1,2-(o)-benzoquinone

VAN:

Vinylanthracene

VPPy:

2-(4-Vinylphenyl)pyridine

VTMS:

Vinyltrimethylsilane

WAXS:

Wide-angle X-ray scattering

Rights and permissions

Reprints and permissions

Copyright information

© 2015 Springer Japan

About this chapter

Cite this chapter

Theodosopoulos, G., Pitsikalis, M. (2015). Block Copolymers by Anionic Polymerization: Recent Synthetic Routes and Developments. In: Hadjichristidis, N., Hirao, A. (eds) Anionic Polymerization. Springer, Tokyo. https://doi.org/10.1007/978-4-431-54186-8_12

Download citation

Publish with us

Policies and ethics

Search

Navigation