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ATRP Synthesis and Characterization of μ,αω-allyl-terminated Macromonomers as Precursors for End-linked Gels and Hydrogels

Published online by Cambridge University Press:  15 February 2011

Lucy Vojtova ,
Nicholas J. Turro  and
Jeffrey T. Koberstein
Lucy Vojtova
Affiliation:
Department of Chemical Engineering, Columbia University, 500 West 120th Street, MC 4721, New York, NY 10027, U.S.A.
Nicholas J. Turro
Affiliation:
Department of Chemistry, Columbia University, 3000 Broadway, MC 3119, New York, NY 10027, U.S.A.
Jeffrey T. Koberstein*
Affiliation:
Department of Chemical Engineering, Columbia University, 500 West 120th Street, MC 4721, New York, NY 10027, U.S.A.
*
*To whom correspondence should be addressed. E-mail: [email protected].
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Abstract

Synthesis of α,ω-allyl-terminated telechelic macromonomers based on poly(tert-butyl methacrylate) (poly(t-BMA)) and poly(methacrylic acid) (poly(MAA)) was studied with the aim of preparing end-linked gels and hydrogels. Low molecular weight α-allyl-terminated poly(t-BMA) macromonomers with narrow polydispersities (Mw/Mn = 1.16) were synthesized via controlled atom transfer radical polymerization (ATRP) using a Cu(I)Br/N,N,N',N',N',N'-hexamethyltriethylenetetraamine catalyst system in conjunction with an allyl-2-bromoisobutyrate as the functional initiator. The polymerizations exhibited a linear increase of molecular weight in direct proportion to the monomer conversion and first-order kinetics with respect to monomer concentration. No significant difference was found between using polar or non-polar solvents (tetrahydrofuran or benzene, respectively). Optimization of reaction conditions to obtain the highest degree of active terminal bromine is discussed. Quenching the ATRP reaction with allyltributyltin yielded α,ω-allyl-terminated poly(t-BMA) macromonomers by replacing the terminal bromine with ω-allyl functional group. Poly(MAA) macromonomers were prepared by deprotection of the tert-butyl group from α,ω-allyl-terminated poly(t-BMA) macromonomers using concentrated trifluoroacetic acid at room temperature. Successful synthetic steps were confirmed by 1H NMR, FT-IR and MALDI-TOF MS analyses. The α,ω-allyl-terminated macromonomers were proven to be candidates for further polymerization by forming end-linked, non-soluble gels.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 774: Symposium O – Materials Inspired by Biology , 2003 , O1.8
Copyright
Copyright © Materials Research Society 2003

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