Transformation of macromonomers into ring-opening polymerization macroinitiators: A detailed initiation efficiency study

Zorn, A. M. & Barner-Kowollik, C. (2012) Transformation of macromonomers into ring-opening polymerization macroinitiators: A detailed initiation efficiency study. Journal of Polymer Science, Part A: Polymer Chemistry, 50(12).

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In the present study, n-butyl acrylate macromonomer (BAMM) (M n = 1900 g mol -1; PDI = 1.96) has been synthesized via a high-temperature polymerization process. Subsequently, the olefinic termini of the BAMM have been transformed into a diol via a dihydroxylation process using KMnO 4 as an oxidizing agent. The OH-terminated macroinitiator pBA(OH) 2 has subsequently been employed for the ring-opening polymerization (ROP) of ε-caprolactone via various catalytic systems, that is, organo-(1,5,7-triazabicyclo[4.4.0]dec-5-ene), metal (tin(II) 2-ethylhexanoate), and enzymatic catalysis (Novozym® 435). The obtained pBA-b-pCL block copolymers and the initiation efficiency of the BAMM macroinitiator have been investigated via size exclusion chromatography (SEC), electrospray ionization-mass spectrometry (ESI-MS) hyphenated with SEC and liquid chromatography at the critical conditions of both poly(ε- caprolactone) (pCL) and pBA. The in vitro enzyme catalysis (eROP) approach proved to be the most efficient catalysis system due to minor transesterification side reactions during the polymerization process. However, side reactions such as transesterifications occur in each catalytic system and-while they cannot be suppressed-they can be minimized. The species generated during the eROP process include the desired block copolymer pBA-b-pCL as main species as well as pCL homopolymer and residual macroinitiator pBA(OH) 2. © 2012 Wiley Periodicals, Inc.

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ID Code: 99334
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :2
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), 76128 Karlsruhe, Germany; email:
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Keywords: β-scission, endgroup transformation, enzyme catalysis, high-temperature acrylate polymerization, macromonomers, ring-opening polymerization, size-exclusion chromatography hyphenated with electrospray ionization mass spectrometry, liquid chromatography, Electrospray ionization mass spectrometry, End groups, High temperature, Macro-monomers, Block copolymers, Catalysis, Electrospray ionization, Enzymes, Liquid chromatography, Mass spectrometry, Monomers, Size exclusion chromatography, Tin, Polymerization
DOI: 10.1002/pola.26011
ISSN: 0887624X
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 30 Sep 2016 02:47

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