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Amphiphilic Cross-Linked Networks Produced from the Vulcanization of Nanodomains within Thin Films of Poly(N-vinylpyrrolidinone)-b-Poly(isoprene)

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Jeremy W. Bartels , Peter L. Billings , Biswajit Ghosh§, Marek W. Urban§, C. Michael Greenlief

and Karen L. Wooley*

^† Department of Chemistry

^‡ Department of Radiology

Washington University in Saint Louis, One Brookings Drive, Saint Louis, Missouri 63130-4899

^§ Shelby F. Thames Polymer Science Research Center, School of Polymers and High Performance Materials, The University of Southern Mississippi, Hattiesburg, Mississippi 39406-0001

Department of Chemistry, University of Missouri−Columbia, 601 South College Avenue, Columbia, Missouri 65211-7600

Langmuir, 2009, 25 (16), pp 9535–9544

DOI: 10.1021/la900753r

Publication Date (Web): June 3, 2009

*Corresponding author. Telephone: (314) 935-7136. Fax: (314) 935-9844. E-mail: klwooley@wustl.edu.

Abstract

Diblock copolymers of poly(N-vinylpyrrolidinone) (PNVP) and poly(isoprene) (PIp) were employed as building blocks for the construction of complex cross-linked networks that present surfaces having amphiphilic character, imparted by covalent trapping of compositionally heterogeneous phase-separated morphologies. The kinetics for the homopolymerization of N-vinylpyrrolidinone by reversible addition−fragmentation chain transfer (RAFT) techniques was studied, and the initially obtained PNVP-based macro-RAFT agents were then extended to PNVP-b-PIp block copolymers. Therefore, the PNVP chain length was held constant at a number-averaged degree of polymerization of 120, while the PIp chain length was varied to afford a series of three PNVP₁₂₀-b-PIp_x block copolymers (where x = 710, 53, and 25). These materials were then cross-linked individually using sulfur monochloride, to produce complex amphiphilic networks. The nanoscopically resolved topographies of these films were analyzed using atomic force microscopy, and their compositional heterogeneities were probed by X-ray photoelectron spectroscopy and internal reflectance infrared imaging techniques. Additionally, the surfaces were analyzed to determine the extent of surface reorganization under aqueous conditions.

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End-Linked Semifluorinated Amphiphilic Polymer Conetworks: Synthesis by Sequential Reversible Addition−Fragmentation Chain Transfer Polymerization and Characterization
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History

Published In Issue August 18, 2009
Article ASAPJune 03, 2009
Received: March 03, 2009
Revised: May 12, 2009

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Article

Amphiphilic Cross-Linked Networks Produced from the Vulcanization of Nanodomains within Thin Films of Poly(N-vinylpyrrolidinone)-b-Poly(isoprene)

Abstract

Citing Articles

One-Pot Synthesis of Natural Rubber-Based Telechelic cis-1,4-Polyisoprenes and Their Use To Prepare Block Copolymers by RAFT Polymerization

One-Pot Synthesis of Natural Rubber-Based Telechelic cis-1,4-Polyisoprenes and Their Use To Prepare Block Copolymers by RAFT Polymerization

End-Linked Semifluorinated Amphiphilic Polymer Conetworks: Synthesis by Sequential Reversible Addition−Fragmentation Chain Transfer Polymerization and Characterization