Copolymerization of allyl butyl ether with acrylates via controlled radical polymerization

Abstract

The atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer (RAFT) of acrylates (methyl acrylate and butyl acrylate) with allyl butyl ether (ABE) were investigated. Well‐defined copolymers containing almost 20 mol % ABE were obtained with ethyl‐2‐bromoisobutyrate as an initiator. Narrow molar mass distributions (MMDs; polydispersity index ≤ 1.3) were obtained from the ATRP experiments, and they suggested conventional ATRP behavior, with no peculiarities caused by the incorporation of ABE. The comparable free‐radical (co)polymerizations resulted in broad MMDs. Increasing the fraction of ABE in the monomer feed led to an increase in the level of incorporation of ABE in the copolymer, at the expense of the overall conversion. Similarly, RAFT copolymerizations with S,S′‐bis(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate also resulted in excellent control of the polymerization with a significant incorporation of ABE within the copolymer chains. The formation of the copolymer was confirmed with matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS). From the obtained MALDI‐TOF MS spectra for the ATRP and RAFT systems, it was evident that several units of ABE were incorporated into the polymer chain. This was attributed to the rapidity of the cross‐propagation of ABE‐terminated polymeric radicals with acrylates. This further indicated that ABE was behaving as a comonomer and not simply as a chain‐transfer agent under the employed experimental conditions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3271–3284, 2004

Experimental Requirements for an Efficient Control of Free‐Radical Polymerizations via the Reversible Addition‐Fragmentation Chain Transfer (RAFT) Process

“…MMA [356] a) [357] Sty [356,358] AA [358] Oct a) [357] DBI [78] MeSty [358] MA [356] ABE a) [359] DCHI [78] EA [358] BA [123,258,345,358] a) [357,359] EHA [358] HEA [358] Am [103,360] tBAm [358] DMAm [360] …”

Novel polymers based on atom transfer radical polymerization of 2‐methoxyethyl acrylate

“…In recent years, numerous different acrylate monomers have also been homo-and block copolymerized by ATRP. [16][17][18][19][20] The purpose of this work is to study the controlled radical homopolymerization of 2-MEA and the possible block copolymerization with methyl methacrylate (MMA) to expand the PMEA material versatility and provide guidelines for the design of novel materials with tailor-made medical device properties.…”

Bio‐based polymer nanocomposites based on layered silicates having a reactive and renewable intercalant

“…This might be ascribed to a maximized interaction between the clay and the polymer matrix most probably due to abovementioned contribution of reactive methacryl and allylic groups of the modifier in the polymerization process. 37,38 It can be clearly seen from the Table III that the storage modulus of the AESOPS1M-C was found to be about 24% higher than that of neat AESOPS matrix. About 400% and 350% increase in storage modulus around T g was achieved as a result of incorporation of 2 wt % and 3 wt % of OrgMMT clay into the AESOPS matrix, respectively.…”