Copolymerizations of butyl methacrylate and fluorinated methacrylates via RAFT miniemulsion polymerization

Abstract

Copolymerizations of n-butyl methacrylate (BMA) and fluoro-methacrylates (including 2,2,3,4,4,4-hexafluorobutyl methacrylate, HFBMA and 2,2,2-trifluoroethyl methacrylate, TFEMA) were carried out via reversible addition-fragmentation chain transfer miniemulsion polymerization, using cumyl dithiobenzoate as a chain transfer agent. The experimental results show that the copolymerizations exhibit ''living'' fashion, with controlled molecular weights and narrow polydispersities. The reactivity ratios of BMA and fluoromethacrylate in this kind of polymerization system were investigated by size exclusion chromatography and nuclear magnetic resonance, from which the Q-and e-values of HFBMA and TFEMA were calculated. Compared with its corresponding non-fluoric methacrylate, fluorinated methacrylate exhibits higher resonance stability of the radical adducts. The Q-value of fluorinated methacrylate is higher (Q BMA ¼ 0.82 to Q HFBMA ¼ 1.70 and Q EMA ¼ 0.76 to Q TFEMA ¼ 1.01), and e-value is much larger (e BMA ¼ 0.28 to e HFBMA ¼ 1.24 to and e EMA ¼ 0.17 to e TFEMA ¼ 1.29) for its rather unique high electron-withdrawing inductive effect of the fluoroalkyl ester group. The thermal property and the wetting property of copolymers were also discussed. V V C 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5067-5075, 2007

Recent advances in the modification of polyacrylate latexes

“…The reason is that the MMA monomer units distributed in PFMA-r-PMMA latex dilutes the concentration of FMA units at the surface, leading to the increase of the surface energy. Block copolymerizations of n-butyl methacrylate (BMA) and fluoro-methacrylates (including 2, 2, 3, 4, 4, 4-hexafluorobutyl methacrylate, HFBMA and 2,2,2-trifluoroethyl methacrylate, TFEMA) were carried out via reversible addition-fragmentation chain transfer miniemulsion polymerization by Guo [51]. The illustration of polymerization is shown in Fig.…”

“…The electrostatic interaction between cationic polyacrylate particle surface and silica makes it possible for silica to accumulate on the periphery of the latex particles. The sol-gel condensation reaction of silica precursor can be controlled by the surface charge of the co-existing [51], [59], [63], [69], [75] Polyethylene glocol monopnonyl phenyl ether (OP-10) [96], PBMA/SiO 2 [97], and PEA/SiO 2 [98] nanocomposite films were prepared. The results showed that there is a strong interaction between polyacrylate latex particles and the SiO 2 network.…”

“…(2) High concentrations of silica precursors in polyacrylate latex greatly decrease the stability of hybrid latex in sol-gel and storage process, because silica precursors have adverse effect on polymerization [93,94]. (3) The polyacrylate/SiO 2 [44], [49], [71] (Perfluoroalkyl)ethyl methacrylate (FEMA) CH 2 CH COO CH 2 CH 2 C n F 2n+1 [36], [47], [50], [57], [76] Hexafluorobutyl methacrylate (Actyflon-G02 or HFBMA) [44], [51], [59], [63], [69] Trifluoroethyl methacrylate (Actyflon-G03 or TFEMA) [36], [51], [58] m-trifluoromethyl phenylamine C F F F NH 2 [54] Dodecafluoroheptyl methacrylate (Actyflon-G04 or DFHMA) [68] nanocomposite film exhibits poor transparency due to the phase separation between inorganic and organic phases.…”

A new class of acrylated alkyds

“…15,16 These three processes have received the most attention because of their versatility in fabricating complex materials with controlled molecular weights, controlled block locations, and narrow molecular weight distributions. [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Of these three living polymerization methods, RAFT has been reported to be the most diverse in monomer choices. 15 Effective RAFT polymerizations are accomplished in the presence of a chain-transfer agent (CTA), which introduces a functional group that actively participates in a reversible additionfragmentation step.…”

Synthesis of α,ω-vinyl telechelic polyurethane macromonomer and preparation of polyurethane-poly(methyl methacrylate) copolymer emulsions via RAFT emulsion polymerization)

“…Comparing with other LCRP, RAFT polymerization can be easily applicable to a wide range of vinyl monomers at the facile temperature and carried out in homogeneous system (bulk and solution) and heterogeneous system (emulsion and mini-emulsion). [17][18][19][20][21][22][23][24][25][26] Of these RAFT polymerization methods, emulsion polymerizations are of great importance in industrial application as they provide environmental-friendly processes, remove the reaction heat easily during polymerization, and assure the feasible handling of the final product having a low viscosity. So, many researches have been concentrated on RAFT emulsion polymerization.…”