Macro-RAFT agent mediated dispersion polymerization: the monomer concentration effect on the morphology of the in situ synthesized block copolymer nano-objects

Ding, Zhonglin; Gao, Chengqiang; Wang, Shuang; Liu, Hui; Zhang, Wangqing

doi:10.1039/c5py01202c

Cited by 40 publications

(42 citation statements)

References 64 publications

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“…10 Since the insolubility of the blocks increases with the block length extension during the course of polymerization, the amphiphilic diblock copolymers self-assemble into a set of polymer nano-objects. [11][12][13][14][15][16][17] A wide range of well-defined morphologies were produced by the PISA, including spheres, worms, vesicles, concentric vesicles, large-compound vesicles and so on. [18][19][20] Although the PISA has its inherent advantages in terms of versatility and efficiency, it is still a young field for researches and the fundamental understanding of the PISA remains incomplete in several aspects.…”

Section: Introductionmentioning

confidence: 99%

“…[18][19][20] Although the PISA has its inherent advantages in terms of versatility and efficiency, it is still a young field for researches and the fundamental understanding of the PISA remains incomplete in several aspects. 9,16,17,[21][22][23][24][25][26][27] For example, the essential difference between the PISA and traditional self-assembly is unclear; the physical mechanism (equilibrium or non-equilibrium behavior) underlying the balance between the polymerization and self-assembly needs to be explored; and the phase diagrams in the PISA should be mapped out to reproduce the PISA process. Insight into these problems can promote nano-object development from trial-and-error towards knowledge-driven innovation.…”

Section: Introductionmentioning

confidence: 99%

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An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation

Huang

Wang

et al. 2016

Soft Matter

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Polymerization-induced self-assembly is a one-pot route to produce concentrated dispersions of block copolymer nano-objects. Herein, dissipative particle dynamics simulations with a reaction model were employed to investigate the behaviors of polymerization-induced self-assembly. The polymerization kinetics in the polymerization-induced self-assembly were analyzed by comparing with solution polymerization. It was found that the polymerization rate enhances in the initial stage and decreases in the later stage. In addition, the effects of polymerization rate, length of macromolecular initiators, and concentration on the aggregate morphologies and formation pathway were studied. The polymerization rate and the length of the macromolecular initiators are found to have a marked influence on the pathway of the aggregate formations and the final structures. Morphology diagrams were mapped correspondingly. A comparison between simulation results and experimental findings is also made and an agreement is shown. This work can enrich our knowledge about polymerization-induced self-assembly.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation

Huang

Wang

et al. 2016

Soft Matter

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“…S3). Many holes exist on the surface of this LCV . These observations suggest that there was inner wall fusion of small vesicles.…”

Section: Resultsmentioning

confidence: 75%

Surface functionalized nano‐objects from oleic acid‐derived stabilizer via non‐polar RAFT dispersion polymerization

Maiti

Bauri

Nandi

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Surface functionalization in a nanoscopic scaffold is highly desirable to afford nano‐particles with diversified features and functions. Herein are reported the surface decoration of dispersed block copolymer nano‐objects. First, side‐chain double bond containing oleic acid based macro chain transfer agent (macroCTA), poly(2‐(methacryloyloxy)ethyl oleate) (PMAEO), was synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization and used as a steric stabilizer during the RAFT dispersion block copolymerization of benzyl methacrylate (BzMA) in n‐heptane at 70 °C. We have found that block copolymer morphologies could evolve from spherical micelles, through worm to vesicles, and finally to large compound vesicles with the increase of solvophobic poly(BzMA) block length, keeping solvophilic chain length and total solid content constant. Finally, different thiol compounds having alkyl, carboxyl, hydroxyl, and protected amine functionalities have been ligated onto the PMAEO segment, which is prone to functionalization via its reactive double bond through thiol‐ene radical reactions. Thiol‐ene modification reactions of the as‐synthesized nano‐objects retain their morphologies as visualized by field emission‐scanning electron microscopy. Thus, the facile and modular synthetic approach presented in this study allowed in situ preparation of surface modified block copolymer nano‐objects at very high concentration, where renewable resource derived oleate surface in the nanoparticle was functionalized. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 263–273

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“…In RAFT dispersion polymerization, it has been demonstrated that the size and/or morphology of block copolymer nanoassemblies is inherently dependent on the DP or chemical composition of block copolymers . Besides, the polymerization conditions, for example, the monomer concentration, also exert great influence on the morphology of block copolymer nanoassemblies, and high monomer concentration in RAFT dispersion polymerization usually favors synthesis of high order morphology of block copolymer nanoassemblies. Herein, the solid content (monomer concentration) and the DP of the PS block affecting the morphology of the PEG 113 ‐ b ‐PS nanoassemblies in the ICAR ATRP dispersion polymerization are checked.…”

Section: Resultsmentioning

confidence: 99%

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

Wang

Han

Duan

et al. 2018

Macromol. Rapid Commun.

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A versatile method for synthesis of block copolymer nanoassemblies via initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) dispersion polymerization in a low molecular weight poly(ethylene glycol) (PEG) is discussed. This ICAR ATRP dispersion polymerization uses a low concentration of CuBr catalyst, which is stable under atmospheric conditions and is soluble in most polar solvents and employs a polymerization medium of viscous and nonvolatile PEG. Through this ICAR ATRP dispersion polymerization, various block copolymer nanoassemblies, including poly(ethylene glycol)-block-polystyrene, poly(ethylene glycol)-block-poly(methyl methacrylate), and poly(2-hydroxypropyl methacrylate)-block-poly(methyl methacrylate), have been synthesized. The parameters affecting the size and morphology of the block copolymer nanoassemblies are briefly discussed.

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Macro-RAFT agent mediated dispersion polymerization: the monomer concentration effect on the morphology of the in situ synthesized block copolymer nano-objects

Cited by 40 publications

References 64 publications

An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation

An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation

Surface functionalized nano‐objects from oleic acid‐derived stabilizer via non‐polar RAFT dispersion polymerization

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

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