Preparation of star block co-polymers by combination of cationic ring opening polymerization and atom transfer radical polymerization

Authors: Erdogan, Tuba; Bernaerts, Katrien V.; Van Renterghem, Lieven M.; Du Prez, Filip E.; Goethals, Eric J.

Source: Designed Monomers & Polymers, Volume 8, Number 6, 2005 , pp. 705-714(10)

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Abstract:

The synthesis of star block co-polymers with polytetrahydrofuran (PTHF) core and poly(tert-butyl acrylate) (PtBA) shell was performed using a dual initiator, 4-hydroxy butyl bromoisobutyrate, by combination of cationic ring-opening polymerization (CROP) and atom transfer radical polymerization (ATRP). The in situ reaction of the hydroxyl groups originating from the dual initiator with trifluoromethane sulfonic anhydride provides a triflate ester initiating group for the CROP of THF. PTHF star polymers having three arms with tertiary bromide end groups (PTHF)₃ have been prepared by reaction of living PTHF chains with tris(2-aminoethyl)amine (TAEA) in the presence of 2,2,6,6-tetramethylpiperidine (TMP) as a proton trap. Subsequently, the star polymers were used as macroinitiators for the ATRP of tBA using the CuBr/N,N,N prime

-pentamethyldiethylenetriamine (PMDETA) catalyst system to obtain the tri-armed star block co-polymers (PTHF-b-PtBA)₃. The polymers were characterized with gel-permeation chromatography (GPC) and¹H-NMR. Both techniques demonstrated the formation of tri-armed star block co-polymers.

Keywords: ATOM TRANSFER RADICAL POLYMERIZATION (ATRP); CATIONIC RING-OPENING POLYMERIZATION (CROP); STAR BLOCK CO-POLYMER; POLYTETRAHYDROFURAN; POLY(TERT-BUTYL ACRYLATE)

Document Type: Research article

DOI: http://dx.doi.org/10.1163/156855505774597812

Publication date: 2005-12-01