In Situ Synthesis of Block Copolymer Nanoassemblies via Polymerization-Induced Self-Assembly in Poly(ethylene glycol)

Abstract

A new formulation of polymerization-induced self-assembly in poly(ethylene glycol) (PEG) named PEG-PISA to synthesize diblock copolymer nanoassemblies via macromolecular RAFT agent mediated dispersion polymerization is reported. In PEG-PISA, the viscous PEG with molecular weight ranging from 200 to 1000 Da is used as polymerization medium. The utilization of the viscous PEG as the polymerization medium affords the advantages including fast polymerization rate, good control over the synthesis of diblock copolymers, and in situ synthesis of both amphiphilic and doubly hydrophobic diblock copolymer nanoassemblies at polymer concentration of up to 50%. Also ascribed to the viscous polymerization medium of PEG, two new and/or interesting diblock copolymer nanoassemblies of ellipsoidal vesicles and nanotubes are formed via PEG-PISA, and the reason on formation of ellipsoidal vesicles and nanotubes is discussed. The proposed PEG-PISA is anticipated to be an effective method to synthesize block copolymer nanoassemblies combining the advantages of alcoholic/aqueous PISA and versatility of poly(ethylene glycol).

ICAR ATRP in PEG with Low Concentration of Cu(II) Catalyst: A Versatile Method for Synthesis of Block Copolymer Nanoassemblies under Dispersion Polymerization

“…Note: PMMA with short chain length is somewhat soluble in PEG400 as discused in ref. , and when DP of the PMMA block increases to about 290 it becomes insoluble at case of concentrated concentration just in the present study and thefore forms block copolymer nanoassemblies.…”

“…Employing volatile organic solvents in synthesis of block copolymer nanoassemblies via RAFT dispersion polymerization is maybe the other factor besides the colored polymers to hinder its wide application. Correspondingly, some high boiling point solvents including ionic solvent and poly(ethylene glycol) (PEG) as polymerization media have been proposed for synthesis of block copolymer nanoassemblies via RAFT dispersion polymerization. PEG is a desirable solvent with low volatility as well as nontoxicity, nonflammability, cheapness, and easy degradability, and it is found that RAFT dispersion polymerization in PEG runs faster than in alcoholic solvent, and this RAFT dispersion polymerization in PEG also leads to synthesis of block copolymer nanoassemblies with complex morphology …”

Self-Assembly of Organic Nanomaterials and Biomaterials: The Bottom-Up Approach for Functional Nanostructures Formation and Advanced Applications

“…Together with the vesicles, nanospheres, worms and lamellaes aggregates, two new morphologies of nanotubes and ellipsoidal vesicles have been prepared from the PNIPAM-b-PS diblock copolymer system as evidenced in by the images of the scanning electron microscopy (SEM) ( Figure 10A-E)) and transmission electron microscopy (TEM) ( Figure 10F). Figure 10G reports the corresponding formation mechanism proposed for the nanotubes and ellipsoidal vesicles aggregates under PEG-PISA approach [97]. Finally, a critical issue in the self-assembly processes involving the block copolymer is represented by morphology instability induced in the nano-assemblies by the presence of given amounts of surfactants.…”

“…Recently, a PISA formulation via dispersion RAFT polymerization in poly(ethylene glycol) (PEG) was proposed for the synthesis of a large variety of amphiphilic diblock copolymer systems, [97]. This PEG-PISA approach provides a good control over the (fast) in situ synthesis of highly concentrated (20-50 wt %) diblock copolymer.…”

Self-assembly synthesis of solid polymer electrolyte with carbonate terminated poly(ethylene glycol) matrix and its application for solid state lithium battery

“…Polymerization-induced self-assembly (PISA) is a very efficient and convenient method to in situ synthesize block copolymer nano-assemblies with controlled size and morphology [37] . Recently, our group has reported a new formulation of PISA called PEG-PISA to synthesize block copolymer nano-assemblies through RAFT dispersion polymerization [38] . In PEG-PISA, the synthesis of block copolymer nano-assemblies is performed in PEG, and therefore traditional organic solvents such as alcohol and alkane are not necessary.…”