Poly(tert-butyl acrylate-b-isobutylene-b-styrene) Terpolymer From a Carbocationic Initiator Containing a Latent Radical Initiating Site
Polymers and High Performance Materials
A poly(isobutylene-b-styrene) (PIB-PS) copolymer was synthesized via quasi-living carbocationic polymerization from an initiator containing a latent site for atom transfer radical polymerization (ATRP) initiation. The initiator, 3.3,5-trimethyl-5-chlorohexyl acetate (TMCHA), was synthesized in four steps from methyl 3,3-dimethyl-4-pentenoate. The PIB block was created at -70 degrees C in a methylcyclohexane/methyl chloride (60:40) cosolvent system, using TiCl4 as the catalyst, followed by sequential addition of styrene. The acetate head group of the resulting block copolymer was converted to a hydroxyl group using a strong base and subsequently esterified with 2-bromopropionyl bromide to create an initiating site for ATRP of tert-butyl acrylate, which was carried out using a Cu(I)Br/1,1,4,7,7,-pentamethyl-diethylenetriamine (PMDETA) catalyst system. The final terpolymers had compositions that were very close to theoretical. (c) 2006 Elsevier Ltd. All rights reserved.
Breland, L. K.,
Murphy, J. C.,
Storey, R. F.
(2006). Poly(tert-butyl acrylate-b-isobutylene-b-styrene) Terpolymer From a Carbocationic Initiator Containing a Latent Radical Initiating Site. Polymer, 47(6), 1852-1860.
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