Skip to main content
SpringerLink
Log in

Novel thermoresponsive block copolymers having different architectures—structural, rheological, thermal, and dielectric investigations

  • Original Contribution
  • Published:
Colloid and Polymer Science Aims and scope Submit manuscript

Abstract

Thermoresponsive block copolymers comprising long, hydrophilic, nonionic poly(methoxy diethylene glycol acrylate) (PMDEGA) blocks and short hydrophobic polystyrene (PS) blocks are investigated in aqueous solution. Various architectures, namely diblock, triblock, and starblock copolymers are studied as well as a PMDEGA homopolymer as reference, over a wide concentration range. For specific characterization methods, polymers were labeled, either by partial deuteration (for neutron scattering studies) or by fluorophores. Using fluorescence correlation spectroscopy, critical micellization concentrations are identified and the hydrodynamic radii of the micelles, r mic h , are determined. Using dynamic light scattering, the behavior of r mic h in dependence on temperature and the cloud points are measured. Small-angle neutron scattering enabled the detailed structural investigation of the micelles and their aggregates below and above the cloud point. Viscosity measurements are carried out to determine the activation energies in dependence on the molecular architecture. Differential scanning calorimetry at high polymer concentration reveals the glass transition of the polymers, the fraction of uncrystallized water and effects of the phase transition at the cloud point. Dielectric relaxation spectroscopy shows that the polarization changes reversibly at the cloud point, which reflects the formation of large aggregates upon heating through the cloud point and their redissolution upon cooling.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Heskins M, Guillet JE (1968) Solution properties of poly(N-isopropylacrylamide). J Macromol Sci Chem A 2:1441–1455

    Article  CAS  Google Scholar 

  2. Aseyev V, Tenhu H, Winnik FM (2011) Non-ionic thermoresponsive polymers in water. Adv Polym Sci 242:29–89

    Article  CAS  Google Scholar 

  3. Gorelov AV, Du Chesne A, Dawson KA (1997) Phase separation in dilute solutions of poly(N-isopropylacrylamide). Physica A 240:443–452

    Article  CAS  Google Scholar 

  4. Aseyev V, Hietala S, Laukkanen A, Nuopponen M, Confortini O, Du Prez FE, Tenhu H (2005) Mesoglobules of thermoresponsive polymers in dilute aqueous solutions above the LCST. Polymer 46:7118–7131

    Article  CAS  Google Scholar 

  5. Schild HG (1992) Poly(N-isopropylacrylamide): experiment, theory and application. Prog Polym Sci 17:163–249

    Article  CAS  Google Scholar 

  6. Maeda Y, Higuchi T, Ikeda I (2001) FTIR spectroscopic and calorimetric studies of the phase transitions of N-isopropylacrylamide copolymers in water. Langmuir 17:7535–7539

    Article  CAS  Google Scholar 

  7. Okada Y, Tanaka F (2005) Cooperative hydration, chain collapse, and flat LCST behavior in aqueous poly(N-isopropylacrylamide) solutions. Macromolecules 38:4465–4471

    Article  CAS  Google Scholar 

  8. Philipp M, Kyriakos K, Silvi L, Lohstroh W, Petry W, Krüger JK, Papadakis CM, Müller-Buschbaum P (2014) From molecular dehydration to excess volumes of phase separating PNIPAM solutions. J Phys Chem B 118:4253–4260

    Article  CAS  Google Scholar 

  9. Wang X, Qiu X, Wu C (1998) Comparison of the coil-to-globule and the globule-to-coil transitions of a single poly(N-isopropylacrylamide) homopolymer chain in water. Macromolecules 31:2972–2976

    Article  CAS  Google Scholar 

  10. Meier-Koll A, Pipich V, Busch P, Papadakis CM, Müller-Buschbaum P (2012) Phase separation in semidilute aqueous poly(N-isopropylacrylamide) solutions. Langmuir 28:8791–8798

    Article  CAS  Google Scholar 

  11. Philipp M, Müller U, Aleksandrova R, Sanctuary R, Müller-Buschbaum P, Krüger JK (2013) Immense elastic nonlinearities at the demixing transition of aqueous PNIPAM solutions. Soft Matter 9:5034–5041

    Article  CAS  Google Scholar 

  12. Miasnikova A, Laschewsky A (2012) Influencing the phase transition temperature of poly(methoxy diethylene glycol acrylate) by molar mass, end groups, and polymer architecture. J Polym Sci A Polym Chem 50:3133–3323

    Article  Google Scholar 

  13. Miasnikova A, Laschewsky A, De Paoli G, Papadakis CM, Müller-Buschbaum P, Funari SS (2012) Thermoresponsive hydrogels from symmetrical triblock copolymers poly(styrene-block-(methoxy diethylene glycol acrylate)-block-styrene). Langmuir 28:4479–4490

    Article  CAS  Google Scholar 

  14. Zhang W, Zhou X, Li H, Fang Y, Zhang G (2005) Conformational transition of tethered poly(N-isopropylacrylamide) chains in coronas of micelles and vesicles. Macromolecules 38:909–914

    Article  CAS  Google Scholar 

  15. Zhou X, Ye X, Zhang G (2007) Thermoresponsive triblock copolymer aggregates investigated by laser light scattering. J Phys Chem B 111:5111–5115

    Article  CAS  Google Scholar 

  16. Troll K, Kulkarni A, Wang W, Darko C, Bivigou Koumba AM, Laschewsky A, Müller-Buschbaum P, Papadakis CM (2008) The collapse transition of poly(styrene-b-(N-isopropyl acrylamide)) diblock copolymers in aqueous solution and in thin films. Colloid Polym Sci 286:1079–1092

    Article  CAS  Google Scholar 

  17. Adelsberger J, Kulkarni A, Jain A, Wang W, Bivigou-Koumba AM, Busch P, Pipich V, Holderer O, Hellweg T, Laschewsky A, Müller-Buschbaum P, Papadakis CM (2010) Thermoresponsive PS-b-PNIPAM-b-PS micelles: aggregation behavior, segmental dynamics, and thermal response. Macromolecules 43:2490–2501

    Article  CAS  Google Scholar 

  18. Adelsberger J, Meier-Koll A, Bivigou-Koumba AM, Busch P, Holderer O, Laschewsky P, Müller-Buschbaum P, Papadakis CM (2011) The collapse transition and the segmental dynamics in concentrated micellar solutions of P(S-b-NIPAM) diblock copolymers. Colloid Polym Sci 289:711–720

    Article  CAS  Google Scholar 

  19. Adelsberger J, Shen X, Bivigou-Koumba AM, Miasnikova A, Golosova A, Funari SS, Busch P, Laschewsky A, Müller-Buschbaum P, Papadakis CM. Poly(styrene-block-(methoxy diethylene glycol acrylate)-block-styrene) triblock copolymers—a combined SAXS and SANS study of the switching behaviour. In revision

  20. Zhong Q, Adelsberger J, Niedermeier MA, Golosova A, Bivigou-Koumba AM, Laschewsky A, Funari SS, Papadakis CM, Müller-Buschbaum P (2013) The influence of selective solvents on the transition behavior of poly(styrene-b-monomethoxydiethylenglycol-acrylate-b-styrene) thick films. Colloid Polym Sci 291:1439–1451

    Article  CAS  Google Scholar 

  21. Zhong Q, Metwalli E, Rawolle M, Kaune G, Bivigou-Koumba AN, Laschewsky A, Papadakis CM, Cubitt R, Müller-Buschbaum P (2013) Structure and thermal response of thin thermoresponsive polystyrene-block-poly(methoxydiethylene glycol acrylate)-block-polystyrene films. Macromolecules 46:4069–4080

    Article  CAS  Google Scholar 

  22. Laschewsky A, Müller-Buschbaum P, Papadakis CM (2013) Thermo-responsive amphiphilic di- and triblock copolymers based on poly(N-isopropylacrylamide) and poly(methoxy diethylene glycol acrylate): aggregation and hydrogel formation in bulk solution and in thin films. Prog Colloid Polym Sci 140:15–34

  23. Nguyen T, Francis MB (2003) Practical synthetic route to functionalized rhodamine dyes. Org Lett 5:3245–3248

    Article  CAS  Google Scholar 

  24. Skrabania K, Miasnikova A, Bivigou-Koumba AM, Zehm D, Laschewsky A (2011) Examining the UV–vis absorption of RAFT chain transfer agents, and their use for polymer analysis. Polym Chem 2:2074–2083

    Article  CAS  Google Scholar 

  25. Widengren J, Mets Ü, Rigler R (1995) Fluorescence correlation spectroscopy of triplet states in solution: a theoretical and experimental study. J Phys Chem 99:13368–13379

    Article  CAS  Google Scholar 

  26. Magde D, Elson EL, Webb WW (1974) Fluorescence correlation spectroscopy. An experimental realization. Biopolymers 13:29–61

    Article  CAS  Google Scholar 

  27. Jakeš J (1988) Czech J Phys B 38:1305–1316

    Article  Google Scholar 

  28. Bartlett P, Ottewill RH (1992) A neutron scattering study of the structure of a bimodal colloidal crystal. J Chem Phys 96:3306–3318

    Article  CAS  Google Scholar 

  29. Percus JK, Yevick GJ (1958) Analysis of classical statistical mechanics by means of collective coordinates. Phys Rev 110:1–13

    Article  CAS  Google Scholar 

  30. Kinning DJ, Thomas EL (1984) Hard-sphere interactions between spherical domains in diblock copolymers. Macromolecules 17:1712–1718

    Article  CAS  Google Scholar 

  31. Posselt D, Pedersen JS, Mortensen K (1992) A SANS investigation on absolute scale of a homologous series of base-catalysed silica aerogels. J Non-Cryst Solids 145:128–132

    Article  CAS  Google Scholar 

  32. Schmidt PW (1982) Interpretation of small-angle scattering curves proportional to a negative power of the scattering vector. J Appl Crystallogr 15:567–569

    Article  CAS  Google Scholar 

  33. Kline SR (2006) Reduction and analysis of SANS and USANS data using IGOR Pro. J Appl Crystallogr 39:895–900

    Article  CAS  Google Scholar 

  34. Kremer F, Schönhals A (eds) (2002) Broadband dielectric spectroscopy. Springer, Berlin

    Google Scholar 

  35. Schuch H, Klingler J, Rossmanith P, Frechen T, Gerst M, Feldthusen J, Müller AHE (2000) Characterization of micelles of polyisobutylene-block-poly(methacrylic acid) in aqueous medium. Macromolecules 33:1734–1740

    Article  CAS  Google Scholar 

  36. Humpolíčková J, Procházka K, Hof M, Tuzar Z, Špírková M (2003) Fluorescence correlation spectroscopy using octadecylrhodamine B as a specific micelle-binding fluorescent tag; light scattering and tapping mode atomic force microscopy studies of amphiphilic water-soluble block copolymer micelles. Langmuir 19:4111–4119

    Article  Google Scholar 

  37. Bonné TB, Lüdtke K, Jordan R, Štěpánek P, Papadakis CM (2004) Aggregation behavior of amphiphilic poly(2-alkyl-2-oxazoline) diblock copolymers in aqueous solution studied by fluorescence correlation spectroscopy. Colloid Polym Sci 282:833–843

    Article  Google Scholar 

  38. Loos K, Böker A, Zettl H, Zhang M, Krausch G (2005) Micellar aggregates of amylose-block-polystyrene rod-coil block copolymers in water and THF. Macromolecules 38:873–879

    Article  CAS  Google Scholar 

  39. Bonné TB, Lüdtke K, Jordan R, Papadakis CM (2007) Effect of polymer architecture of amphiphilic poly(2-oxazoline) copolymers on the aggregation and aggregate structure. Macromol Chem Phys 208:1402–1408

    Article  Google Scholar 

  40. Colombani O, Ruppel M, Schubert F, Zettl H, Pergushov DV, Müller AHE (2007) Synthesis of Poly(n-butyl acrylate)-block-poly(acrylic acid) diblock copolymers by ATRP and their micellization in water. Macromolecules 40:4338–4350

    Article  CAS  Google Scholar 

  41. Koynov K, Butt H-J (2012) Fluorescence correlation spectroscopy in colloid and interface science. Curr Opin Colloid Interface Sci 17:377–387

    Article  CAS  Google Scholar 

  42. Wöll D (2014) Fluorescence correlation spectroscopy in polymer science. RSC Adv 4:2447–2465

    Article  Google Scholar 

  43. Bonné TB, Papadakis CM, Lüdtke K, Jordan R (2007) Role of the tracer in characterizing the aggregation behavior of aqueous block copolymer solutions using fluorescence correlation spectroscopy. Colloid Polym Sci 285:491–497

    Article  Google Scholar 

  44. Dean JA (1999) Lange’s Handbook of Chemistry. McGraw-Hill, New York, p 6.115

  45. Panagopoulou A, Kyritsis A, Aravantinou AM, Nanopoulos D, Sabater i Serra R, Gómez Ribellez JL, Shinyashiki N, Pissis P (2011) Glass transition and dynamics in lysozyme-water mixtures over wide ranges of composition. Food Biophys 6:199–209

    Article  Google Scholar 

  46. Bordi F, Cametti C, Colby RH (2004) Dielectric spectroscopy and conductivity of polyelectrolyte solutions. J Phys Condens Matter 16:R1423–R1463

    Article  CAS  Google Scholar 

  47. Masci G, Ladogana RD, Cametti C (2011) Assemblies of thermoresponsive diblock copolymers: micelle and vesicle formation investigated by means of dielectric relaxation spectroscopy. J Phys Chem B 115:2196–2204

    Article  CAS  Google Scholar 

  48. Zhou J, Wei J, Ngai T, Wang L, Zhu D, Shen J (2012) Correlation between dielectric/electric properties and cross-linking/charge density distributions of thermally sensitive spherical PNIPAM microgels. Macromolecules 45:6158–6167

    Article  CAS  Google Scholar 

  49. Füllbrandt M, von Klitzing R, Schönhals A (2013) The dielectric signature of poly(N-isopropylacrylamide) microgels at the volume phase transition: dependence on the crosslinking density. Soft Matter 9:4464–4471

    Article  Google Scholar 

Download references

Acknowledgments

We thank Katerina Bikas for the help with the DLS experiments. This work was supported by Deutsche Forschungsgemeinschaft (DFG) within the priority program SPP1259 “Intelligente Hydrogele” (grants Pa771/4, Mu1487/8, La611/7). We gratefully acknowledge Bavarian Research Alliance for a travel grant within the “Bavarian Funding Programme for the Initiation of International Projects” as well as Deutscher Akademischer Austauschdienst for the travel support within the program “Hochschulpartnerschaften mit Griechenland”. Portions of this research were carried out at the KWS-2 instrument operated by JCNS at the Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRM II), Garching, Germany.

Author information

Authors and Affiliations

  1. Physik-Department, Fachgebiet Physik weicher Materie/Lehrstuhl Physik funktioneller Materialien, Technische Universität München, James-Franck-Str. 1, 85748, Garching, Germany

    Konstantinos Kyriakos, Lukas Augsbach, Josef Sapper, Sarah Ottinger, Christina Psylla, Ali Aghebat Rafat, Peter Müller-Buschbaum & Christine M. Papadakis

  2. Physics Department, National Technical University of Athens, Iroon Polytechneiou 9, Zografou Campus, Athens, 15780, Greece

    Dionysia Aravopoulou & Apostolos Kyritsis

  3. Institut für Chemie, Universität Potsdam, Karl-Liebknecht-Str. 24-25, 14476, Potsdam-Golm, Germany

    Carlos Adrian Benitez-Montoya, Anna Miasnikova & André Laschewsky

  4. Jülich Centre for Neutron Science (JCNS), Forschungszentrum Jülich GmbH, Outstation at MLZ, Lichtenbergstr. 1, 85748, Garching, Germany

    Zhenyu Di

  5. Fraunhofer Institut für Angewandte Polymerforschung, Geiselbergstr. 69, 14476, Potsdam-Golm, Germany

    André Laschewsky

Authors
  1. Konstantinos Kyriakos
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dionysia Aravopoulou
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Lukas Augsbach
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Josef Sapper
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Sarah Ottinger
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Christina Psylla
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Ali Aghebat Rafat
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Carlos Adrian Benitez-Montoya
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Anna Miasnikova
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Zhenyu Di
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. André Laschewsky
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Peter Müller-Buschbaum
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Apostolos Kyritsis
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Christine M. Papadakis
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Christine M. Papadakis.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kyriakos, K., Aravopoulou, D., Augsbach, L. et al. Novel thermoresponsive block copolymers having different architectures—structural, rheological, thermal, and dielectric investigations. Colloid Polym Sci 292, 1757–1774 (2014). https://doi.org/10.1007/s00396-014-3282-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00396-014-3282-0

Keywords

Search

Navigation