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Colloid and Polymer Science

, Volume 289, Issue 5–6, pp 497–512 | Cite as

Combination of living anionic polymerization and ATRP via “click” chemistry as a versatile route to multiple responsive triblock terpolymers and corresponding hydrogels

  • Stefan Reinicke
  • Holger SchmalzEmail author
Original Contribution

Abstract

A combination of anionic polymerization, atom transfer radical polymerization (ATRP) and “click” chemistry was used to construct trishydrophilic ABC triblock terpolymers composed of a pH-sensitive A block, a water-soluble B block and two different thermo-sensitive C blocks without any block sequence limitation problems. First, an azido end-functionalized poly(2-vinylpyridine)-block-poly(ethylene oxide) (P2VP-b-PEO-N3) diblock copolymer was synthesized by anionic polymerization. In a second step, poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and poly(oligo(ethylene glycol) methacrylate) (POEGMA) were synthesized via ATRP using an alkyne functionalized initiator. The resulting polymers were attached to the P2VP-b-PEO-N3 diblock copolymer using the 1,3-dipolar Huisgen cycloaddition (“click” chemistry). For the “click” step, P2VP-b-PEO-N3 diblock copolymers with either an azidoacetyl or a 2-azidoisobutyryl group were tested. In the latter case, however, a side reaction involving the cleavage of the formed “click” product via nucleophilic substitution occurred, preventing a permanent attachment of PDMAEMA or POEGMA to the P2VP-b-PEO-N3 diblock copolymer. Finally, P2VP-b-PEO-b-POEGMA (with POEGMA=P(MEO2MA-co-MEO8.5MA)) and P2VP-b-PEO-b-PDMAEMA triblock terpolymers were successfully synthesized and used to construct stimuli-responsive hydrogels. A concentrated solution of P2VP56-b-PEO370-b-P[(MEO2MA)89-co-(MEO8.5MA)7] showed a gel–sol–gel transition at pH 7 upon temperature increase, whereas in the case of P2VP56-b-PEO370-b-PDMAEMA70, a gel–sol or a weak gel–strong gel transition was observed, depending on the applied pH. Finally, the addition of trivalent hexacyanocobaltate(III) ions to the P2VP56-b-PEO370-b-PDMAEMA70 solution induced an upper critical solution temperature for the PDMAEMA block, which led to gel formation. This allows for the construction of light-sensitive hydrogels, utilizing the photo-aquation of hexacyanocobaltate(III) ions.

Keywords

Anionic polymerization “Click” chemistry Triblock terpolymer Multi-responsive hydrogel Light sensitivity Rheology 

Notes

Acknowledgement

We would like to thank Ingo Rehberg and Reinhard Richter (Experimental Physics V, University of Bayreuth) for providing us with the rheology equipment, Marietta Böhm (MCII, University of Bayreuth) for conducting the SEC measurements, and Felix Plamper (RWTH Aachen) for helpful discussion. Financial support from the German Science Foundation (priority programme SPP 1259) is gratefully acknowledged.

Supplementary material

396_2010_2359_MOESM1_ESM.pdf (290 kb)
ESM 1 (PDF 289 kb)

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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  1. 1.Makromolekulare Chemie IIUniversität BayreuthBayreuthGermany

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