Syntheses of 2-(trifluoromethyl)acrylate-containing block copolymers via RAFT polymerization using a universal chain transfer agent

Abstract

2-(Trifluoromethyl)acrylate-containing block copolymers were synthesized via RAFT polymerization using a universal CTA.

Fluoroalkyl Pentacarbonylmanganese(I) Complexes as Initiators for the Radical (co)Polymerization of Fluoromonomers

“…Four copolymerizations of vinyl acetate (VAc) and tert-butyl 2-(trifluoromethyl)acrylate (MAF-TBE) were carried out using compounds 3 and 6 as initiators (Scheme II). This copolymer was previously synthesized by conventional [41] OMRP using cobalt(II) acetylacetonate as a controlling agent [42] and RAFT polymerization [43]. All these four co-polymerizations led to copolymers, which display a perfectly alternating structure, in agreement with the measured reactivity ratios that are both close to zero [41].…”

Synthesis of Biobased Block Copolymers Using A Novel Methacrylated Methyl Salicylate and Poly(3‐Hydroxybutyrate)

“…RAFT polymerization is a versatile process that, with appropriate selection of reagents and reaction conditions, satisfies most of the established criteria for living polymerization. [34][35][36][37][38][39][40][41][42] The obtained macro RAFT agents were used in the RAFT polymerizations of methacrylated methyl salicylate (KzSA-MA) in the presence of AIBN to yield PHB-b-KzSA-MA block copolymers. The polymerization conditions and the results were shown in Table 1.…”

Synthesis, aqueous solution behavior and self-assembly of a dual pH/thermo-responsive fluorinated diblock terpolymer

“…The P(VAc-alt-MAF-TBE) RAFT macroCTA was synthesized using a procedure similar to that described previously. 49 A typical procedure (Scheme 1-a) is described below: MAF-TBE (12.51 g, 63.70 mmol), VAc (5.49 g, 63.70 mmol), CDPCD (0.50 g, 2.70 mmol) and V-70 (73.00 mg, 0.20 mmol) were added in a 100 ml round bottom flask equipped with a magnetic stirrer under a nitrogen flow. Subsequently, the flask was sealed with a rubber septum and the reaction mixture was stirred for 20 min at ambient temperature.…”

“…The P(VAc-alt-MAF-TBE) macroCTA was synthesized using a procedure similar to that described in a previous article. 49 MAF-TBE is a fluorinated monomer which has been studied for specific materials in lithium ion batteries, fuel cell membranes and photoresist lithography. [50][51][52][53][54] A main characteristic of alkyl 2-trifluoromethyl acrylates (and hence of MAF-TBE) is that they do not homopolymerize under radical conditions, 55,56 while anionic polymerization is successful.…”

“…The ability of P(VAc-alt-MAF-TBE) copolymer to serve as macroCTA for the successful synthesis of diblock terpolymers via RAFT was evidenced in a previous article. 49 Here, DMA and NIPAM were chosen as monomers for the synthesis of P(VAc-alt-MAF-TBE)-b-PDMA and P(VAc-alt-MAF-TBE)-b-PNIPAM diblock terpolymers, respectively (Table 1, entries 2-5). The successful syntheses of these diblock terpolymers were clearly evidenced by GPC and NMR spectroscopy. )…”