Comparative study of classical surfactants and polymerizable surfactants (surfmers) in the reversible addition–fragmentation chain transfer mediated miniemulsion polymerization of styrene and methyl methacrylate

Abstract

Cationic and anionic amphiphilic monomers (surfmers) were synthesized and used to stabilize particles in miniemulsion polymerization. A comparative study of classical cationic and anionic surfactants and the two surfmers was conducted with respect to the reaction rates and molecular weight distributions of the formed polymers. The reversible addition–fragmentation chain transfer process was used in the miniemulsion polymerization reactions to control the molecular weight distribution. The reaction rates of the surfmer‐stabilized miniemulsion polymerization of styrene and methyl methacrylate were similar (in most cases) to those of the classical‐surfactant‐stabilized miniemulsion polymerizations. The final particle sizes were also similar for polystyrene latexes stabilized by the surfmers and classical surfactants. However, poly(methyl methacrylate) latexes stabilized by the surfmers had larger particle sizes than latexes stabilized by classical surfactants. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 427–442, 2006

Living Radical Polymerization by the RAFT Process—A First Update

“…76), are effective with styrenic and acrylic monomers. Recent work [54,55] has focussed on the relative effectiveness of a series of dithiocarbamates where the nitrogen lone pair is part of a heteroaromatic ring system (78)(79)(80)(81)(82)(83)(84)(85) in controlling polymerization of styrene. Of these, compounds 84 and 85, where there is little delocalization of the lone pair into the aromatic system, were not effective as RAFT agents.…”

“…10* EEA [77] BMA [78] BzA [78] 11* (DBI) [64] DMA [72] HPMAM [80] 12a* R = H BzMA [78] DMAEMA [78] EHA [78] MMA [81] PEGMA [72] PFMA [73] S [81] 12b R = CH 3 [83] AM [83] TMAEMA [83] MA [78] MMA [78,79] tBA [78] XMA [82] S…”

“…A large number of recent studies relate RAFT polymerization in heterogeneous media (emulsion, [67,74,81,98,117,122,139,[161][162][163][164][165][166] miniemulsion, [10,76,[167][168][169][170][171][172][173][174][175] or suspension [176] ). The area has been reviewed by McCleary and Klumperman [11] and Save et al [177] 'Surfactant free' emulsion polymerization making use of a hydrophilic macroRAFT agent (typically based on PAA oligomer formed with RAFT agent 67) [117,161,163,164] has been used for BA [117] and styrene.…”

Polimerização RAFT em Miniemulsão

“…A Tabela 1 apresenta os estudos publicados até a presente data sobre a produção de polímeros que utilizaram a técnica RAFT em miniemulsão. Conforme revisado, a técnica de polimerização RAFT em miniemulsão já foi adaptada para os principais tipos de monômeros comerciais (como, por exemplo, estireno [28,34,35, , metacrilato de metila [35,54,68,[74][75][76][77][78][79][80] ), sistemas inversos [23,52,[81][82][83][84][85][86] e sistemas contínuos de polimerização [87][88][89] ). Além dos trabalhos citados na P(AM-co-AA) Inverso [83] P(NIPAM-b-PEO) Inverso [82] a Poliestireno (PSt), poli(metacrilato de metila) (PMMA), poli(buitl metacrilato (PnBMA), poli(hidroxietil metacrilato) (PEHMA), poli(butil acrilato) (PnBA), poli(acetato de vinila) (PVAc), Poliacrilamida (PAM), poli(ácido acrílico), poli(2-dimetilamino (metacrilato de etila)) (PDMAEMA), ácido metacrílico (MAA), acrilato de dodecafluoro heptil (DFHA), acrilamida (AM), ácido acrílico (AA), isopopil acrilamida (NIPAM), poli(óxido de etileno) (PEO).…”

A Green Approach for the Synthesis of Fluorescent Polymer Particles by Combined Use of Enzymatic Miniemulsion Polymerization with Clickable Surfmer and Click Reaction

“…These results spurred us to explore the feasibility of using reactive surfmer, i.e., alkyne-bearing surfmer, to introduce the alkyne moieties onto the surface of polymer particles via enzymatic miniemulsion polymerization in a one-pot procedure at room temperature. While there were some pioneer works of miniemulsion polymerization with a functional surfmer to prepare polymer particles [24][25][26][27][28][29][30][31], only one study on post-functionalization of particles surface based on surfmer was found in the literature [32]. Froimowicz and Landfester reported that the preparation of particles by miniemulsion polymerization with phosphonate surfmer, and phosphonate functionalized obtained particles were used as functional scaffolds allowing the binding of calcium ions to subsequently mineralize hydroxyapatite on the surface of the particles.…”