Aqueous Dispersion Polymerization of 2-Methoxyethyl Acrylate for the Synthesis of Biocompatible Nanoparticles Using a Hydrophilic RAFT Polymer and a Redox Initiator

Abstract

Aqueous dispersion polymerization systems mediated by reversible addition–fragmentation chain transfer (RAFT) process have been less studied in comparison with other heterogeneous polymerization systems due to limited number of monomer/polymer pairs that are suitable for such a condition. We report a novel dispersion polymerization system based on 2-methoxyethyl acrylate (MEA) which is highly water-soluble, but its polymer is not. Using a hydrophilic polymer, poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA), as the macromolecular chain transfer agent (Macro-CTA), both solution and dispersion polymerization of MEA were studied. Chain extension by MEA from PPEGMA was successfully realized in DMF solution polymerization. In dispersion polymerization of MEA in water, PPEGMA was used as both a RAFT mediating species and a steric stabilizer for the formed nanoparticles. The dispersion polymerization of MEA in water was highly efficient using a redox initiator, potassium persulfate/sodium ascorbate, at low temperatures. Simultaneous control of both colloidal stability and RAFT process was realized. Block copolymers with small polydispersity indices were efficiently produced up to complete monomer conversion at solids content up to 32% w/v, in the form of nanoparticles of 40–60 nm diameter.

Living Radical Polymerization by the RAFT Process – A Third Update

“…Nonetheless, the (RAFT) polymerization induced selfassembly and the factors which control what structure is formed have recently attracted considerable interest with studies on the phenomenon in emulsion polymerization, [354,381,400] dispersion polymerization [187,224,229,353,361,571] and non-aqueous dispersion polymerization. [394,397] Blanazs et al [187] have constructed a phase diagram for poly(288)-poly(HPMA).…”

“…DMAm [348] DMAm-b-HEAm [348] 97 n ϭ 1 or 2 [349,350] DEAEMA [351] DMAEMA [350,352] PEGMA [224,[353][354][355] (412) [243] PAA [356] DMAm [326] DMAm [326] HPMAm [357] 357 [357] MAA/PEGMA [354] APMAm/DEAPMAm [358] APMAm/DMAPMAm [358] DEAEMA-bNIPAm [351] DMEAEMA-b-NIPAm [359] PEGMA/MAA-b-St [354,360] PEGMA/MAA-bBzMA [361] PEGMA/MAA-b-327 [362] PAA-bDMAm/408 [356] DMAEMA-b-(PAA/BMA/ DMAEMA) [350,352] HPMAm/450/451 [363] HPMAm-b-357 [357] 98 [364] 317 [311] 332 [365] 333 [365] DMAm [366] BA [366] 350 [311] NIPAm [366,367] MAA/ MMA [368] MAA/DFHA [369] OeMA/MMA [364] 332-b-MMA [365] 333-b-MMA [365] NIPAm-bDMAEAm [367] 99…”

“…BA BA TEGMA MBAm [355] [ 355] DMAm 132 DEAm MBAm [571] PEGMA-b-EGMA 173 BA TEGMA [355] PEGMA 97 EGMA TEGMA [353] NIPAm 138 St DVB [419] -158 397 EGDMA [584] -158 -DVB [626] MA 158 -DVB [626] -23 DMAEMA 422 [256] 354 145 St 423 [427] PFPA PFPA PFPA tBA 179 -424 [461] NIPAm 179 -424 [461] A See footnote B of Table 3. cleavable imine linkages (Scheme 27).…”

Characterization of Diblock Copolymer Order-Order Transitions in Semidilute Aqueous Solution Using Fluorescence Correlation Spectroscopy

“…[14][15][16] This versatile approach has enabled spherical, worm-like or vesicular copolymer morphologies to be generated in concentrated solution. [ 11,[17][18][19][20][21][22][23][24][25][26] Such a nonionic PGMA-PHPMA diblock copolymer exhibits a thermoreversibleThe temperature and pH-dependent diffusion of poly(glycerol monomethacrylate)-blockpoly(2-hydroxypropyl methacrylate) nanoparticles prepared via polymerization-induced self-assembly in water is characterized using fl uorescence correlation spectroscopy (FCS). Lowering the solution temperature or raising the solution pH induces a worm-to-sphere transition and hence an increase in diffusion coeffi cient by a factor of between four and eight.…”

“…[14][15][16] This versatile approach has enabled spherical, worm-like or vesicular copolymer morphologies to be generated in concentrated solution. [ 11,[17][18][19][20][21][22][23][24][25][26] Such a nonionic PGMA-PHPMA diblock copolymer exhibits a thermoreversible…”