Self-assembly of gradient copolymers in a selective solvent. New structures and comparison with diblock and statistical copolymers

During the last number of years a variety of crystallization-driven self-assembly (CDSA) processes based on semicrystalline block copolymers have been developed to prepare a number of different nanomorphologies in solution (micelles). We herein present a convenient synthetic methodology combining: (i) The anionic polymerization of 2-vinylpyridine initiated by organolithium functionalized phosphane initiators; (ii) the cationic polymerization of iminophosphoranes initiated by –PR2Cl2; and (iii) a macromolecular nucleophilic substitution step, to prepare the novel block copolymers poly(bistrifluoroethoxy phosphazene)-b-poly(2-vinylpyridine) (PTFEP-b-P2VP), having semicrystalline PTFEP core forming blocks. The self-assembly of these materials in mixtures of THF (tetrahydrofuran) and 2-propanol (selective solvent to P2VP), lead to a variety of cylindrical micelles of different lengths depending on the amount of 2-propanol added. We demonstrated that the crystallization of the PTFEP at the core of the micelles is the main factor controlling the self-assembly processes. The presence of pyridinyl moieties at the corona of the micelles was exploited to stabilize gold nanoparticles (AuNPs).

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A lattice self-consistent field study of self-assembly of grafted ABA triblock copolymers in a selective solvent

Polymer ◽

10.1016/j.polymer.2018.02.046 ◽

2018 ◽

Vol 140 ◽

pp. 278-289 ◽

Cited By ~ 1

Author(s):

Wenjuan Qiu ◽

Zheng Wang ◽

Yuhua Yin ◽

Run Jiang ◽

Baohui Li ◽

...

Keyword(s):

Field Study ◽

Self Assembly ◽

Triblock Copolymers ◽

Selective Solvent ◽

Consistent Field ◽

Self Consistent ◽

Self Consistent Field

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Self-Assembly of Hydrogen-Bonding Gradient Copolymers: Sequence Control via Tandem Living Radical Polymerization with Transesterification

Macromolecules ◽

10.1021/acs.macromol.7b00070 ◽

2017 ◽

Vol 50 (8) ◽

pp. 3215-3223 ◽

Cited By ~ 24

Author(s):

Yusuke Ogura ◽

Müge Artar ◽

Anja R. A. Palmans ◽

Mitsuo Sawamoto ◽

E. W. Meijer ◽

...

Keyword(s):

Hydrogen Bonding ◽

Radical Polymerization ◽

Self Assembly ◽

Living Radical Polymerization ◽

Gradient Copolymers

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Synthesis of CO2-responsive gradient copolymers by switchable RAFT polymerization and their controlled self-assembly

Polymer Chemistry ◽

10.1039/d0py01109f ◽

2020 ◽

Vol 11 (42) ◽

pp. 6794-6802

Author(s):

Xiaofeng Guo ◽

Tianren Zhang ◽

Yuetong Wu ◽

Wencheng Shi ◽

Bonnie Choi ◽

...

Keyword(s):

Self Assembly ◽

Raft Polymerization ◽

Good Control ◽

Acid Base ◽

Gradient Copolymers

Switchable RAFT agents, so-called because they can be reversibly switched by an acid/base stimulus to offer very good control over polymerization of both MAMs and LAMs, provide a route to prepare well-defined polyMAM-block-polyLAM copolymers.

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Self-assembly of linear diblock copolymers in selective solvents: from single micelles to particles with tri-continuous inner structures

Soft Matter ◽

10.1039/d0sm00402b ◽

2020 ◽

Vol 16 (26) ◽

pp. 6056-6062 ◽

Cited By ~ 1

Author(s):

Xianggui Ye ◽

Bamin Khomami

Keyword(s):

Diblock Copolymer ◽

Self Assembly ◽

Large Scale ◽

Diblock Copolymers ◽

Dissipative Particle Dynamics ◽

Particle Dynamics ◽

The Self ◽

Selective Solvent ◽

Selective Solvents

Large-scale dissipative particle dynamics (DPD) simulations have been performed to investigate the self-assembly of over 20 000 linear diblock copolymer chains in a selective solvent.

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Self-assembly in the solutions of poly(methyl methacrylates) end-capped with fluorophenyl groups

e-Polymers ◽

10.1515/epoly.2009.9.1.342 ◽

2009 ◽

Vol 9 (1) ◽

Cited By ~ 1

Author(s):

Ekaterina R. Gasilova ◽

Olga G. Zakharova ◽

Sergey D. Zaitsev ◽

Yury D. Semchikov

Keyword(s):

Self Assembly ◽

Chain Transfer ◽

Photon Correlation Spectroscopy ◽

Correlation Spectroscopy ◽

Selective Solvent ◽

Photon Correlation ◽

Molecular Weights ◽

Methyl Methacrylates ◽

A Chain ◽

Strong Segregation

AbstractSelf-assembly of poly(methyl methacrylates) end-capped with -Ge(C6F5)3 groups (PMMA-F) has been studied in a selective solvent (acetone) by means of photon correlation spectroscopy and static light scattering. PMMA-F’s of different molecular weights (MW), were obtained by radical polymerization in the presence of a chain transfer agent, HGe(C6F5)3. At MW>130 000 conformational and hydrodynamic properties of PMMA-F’s is shown to be the same as of PMMA. At MW less than130 000 an aggregation starts: additional fraction of large scatterers appears in PCS. Large aggregates of Rh=200 - 300 nm are likely to be formed by bridged micellar clusters. Presence of large aggregates indicates a super strong segregation limit predicted in the work of Semenov et al.

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Gradient helical copolymers: synthesis, chiroptical properties, thermotropic liquid crystallinity, and self-assembly in selective organic solvents

Polymer Chemistry ◽

10.1039/c8py00237a ◽

2018 ◽

Vol 9 (15) ◽

pp. 2002-2010 ◽

Cited By ~ 3

Author(s):

Junxian Chen ◽

Bowen Li ◽

Xiaofu Li ◽

Jie Zhang ◽

Xinhua Wan

Keyword(s):

Organic Solvents ◽

Self Assembly ◽

Radical Copolymerization ◽

Atom Transfer ◽

Liquid Crystallinity ◽

Gradient Copolymers ◽

Chiroptical Properties

A series of novel gradient copolymers R-(−)-poly(StN-grad-C8) were synthesized through atom transfer radical copolymerization of an achiral styrenic monomer, N,N-dimethyl-4-ethenylbenzamide (M-StN), and a chiral bulky vinylterphenyl monomer, (−)-2,5-bis{4′-[(R)-sec-octyloxycarbonyl]phenyl}styrene (R-(−)-M-C8).

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