期刊
JOURNAL OF POLYMER SCIENCE
卷 60, 期 4, 页码 666-673出版社
WILEY
DOI: 10.1002/pol.20210658
关键词
ARGET-ATRP; hydrophilicity; mini-emulsion polymerization
资金
- Air Force Office of Scientific Research [FA9550-17-1-0038]
- NSF MRSEC Program, Division of Materials Research [DMR-1719875]
- National Science Foundation [DGE-1650441]
- Air Force Research Laboratory
In this study, aqueous miniemulsion polymerization based on Activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) was used to investigate the effects of hydrophobicity of monomers on dispersity, molecular weight, and particle stability. The results showed that monomers with higher hydrophobicity exhibited narrower dispersity and better control, while monomers with higher hydrophilicity led to reduced emulsion stability. This research provides insights into controlled polymerizations of hydrophilic monomers using ARGET-ATRP in miniemulsion conditions, with implications for synthesis of polymer-grafted nanoparticles with hydrophilic corona.
Activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP)-based aqueous miniemulsion polymerization where the polymerization takes place in the stabilized monomer droplets is described. In this work, we compared styrene, n-butyl methacrylate (nBMA) and tert-butyl methacrylate (tBMA) and investigated the influence of their hydrophobicity on dispersity, molecular weight and particle stability based their partition coefficients (logP) (2.67, 2.23, and 1.86, respectively). Tetrabutylammonium bromide (TBAB) was used as a phase transfer agent for the controlled delivery of Cu2+-Br/tris(2-pyridylmethyl)amine (TPMA), a hydrophilic catalyst, into monomer droplets of varying hydrophobicity. The resulting dispersity and particle stability of each polymer is a function of its logP value, with the most hydrophobic monomer (styrene) displaying the narrowest dispersity and most control (D < 1.3), and the most hydrophilic polymer poly(tert-butyl methacrylate) (PtBMA) having reduced emulsion stability, determined by the observation of aggregate formation. Selected polymerization parameters, including effects of total ascorbic acid feed concentration and the monomer concentration and their effects on dispersity are reported. The controlled polymerizations of hydrophilic monomers using ARGET-ATRP in miniemulsion conditions and understanding the effect of monomer hydrophilicity on the emulsion stability will broaden the use of ARGET-ATRP in emulsion polymerization for the synthesis of polymer-grafted nanoparticles with hydrophilic corona.
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