Publication detail

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

VOJTOVÁ, L. TURRO, N. KOBERSTEIN, J.

Original Title

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

English Title

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

Type

journal article - other

Language

en

Original Abstract

Synthesis of alpha,omega-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 alpha-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/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 alpha,omega-allyl-terminated poly(t-BMA) macromonomers by replacing the terminal bromine with omega-allyl functional group. Poly(MAA) macromonomers were prepared by deprotection of the tert-butyl group from alpha,omega-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.

English abstract

Synthesis of alpha,omega-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 alpha-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/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 alpha,omega-allyl-terminated poly(t-BMA) macromonomers by replacing the terminal bromine with omega-allyl functional group. Poly(MAA) macromonomers were prepared by deprotection of the tert-butyl group from alpha,omega-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.

Keywords

macromonomers, hydrogels, characterization

Released

21.04.2003

Publisher

Materials Research Society

Location

USA

ISBN

0272-9172

Periodical

Materials Research Society symposia proceedings

Year of study

774

Number

O

State

US

Pages from

59

Pages to

73

Pages count

15

Documents

BibTex


@article{BUT50188,
  author="Lucy {Vojtová} and Nicholas {Turro} and Jeffrey T. {Koberstein}",
  title="ATRP Synthesis and Characterization of alpha,omega-allyl-terminated Macromonomers as Precursors for End-linked Gels and Hydrogels",
  annote="Synthesis of alpha,omega-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 alpha-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/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 alpha,omega-allyl-terminated poly(t-BMA) macromonomers by replacing the terminal bromine with omega-allyl functional group. Poly(MAA) macromonomers were prepared by deprotection of the tert-butyl group from alpha,omega-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.",
  address="Materials Research Society",
  chapter="50188",
  institution="Materials Research Society",
  journal="Materials Research Society symposia proceedings",
  number="O",
  volume="774",
  year="2003",
  month="april",
  pages="59--73",
  publisher="Materials Research Society",
  type="journal article - other"
}