Architecture of rod–brush block copolymers synthesized by a combination of coordination polymerization and atom transfer radical polymerization

Ishizu, Koji; Hatoyama, Naomasa; Uchida, Satoshi

doi:10.1002/app.27936

Cited by 4 publications

(3 citation statements)

References 25 publications

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“…Block copolymers have attracted a great deal of interest in physical chemistry and polymer science owing to their precise supramolecular structures in bulk or solution1–4 and potential various applications 3–9. However, perhaps due to the ease of preparation, most attention has focused on coil–coil block copolymers.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and self‐assembly of amphiphilic star‐block copolymers consisting of polyethylene and poly(ethylene glycol) segments

Liu¹,

Li²,

Wang³

et al. 2013

J of Applied Polymer Sci

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We report on the synthesis and self-assembly in water of well-defined amphiphilic star-block copolymers with a linear crystalline polyethylene (PE) segment and two or three poly(ethylene glycol) (PEG) segments as the building blocks. Initially, alkynyl-terminated PE (PE-B) is synthesized via esterification of pentynoic acid with hydroxyl-terminated PE, which is prepared using chain shuttling ethylene polymerization with 2,6-bis[1-(2,6-dimethylphenyl) imino ethyl] pyridine iron (II) dichloride/methylaluminoxane/diethyl zinc and subsequent in situ oxidation with oxygen. Then diazido-and triazido-terminated PE (PE-(N 3 ) 2 and PE-(N 3 ) 3 ) are obtained by the click reactions between PE-B and coupling agents containing triazido or tetraazido, respectively. Finally, the three-arm and four-arm star-block copolymers, PE-b-(PEG) 2 and PE-b-(PEG) 3 , are prepared by click reactions between PE-(N 3 ) 2 or PE-(N 3 ) 3 and alkynyl-terminated PEG. The self-assembly of the resultant amphiphilic star-block copolymers in water was investigated by dynamic light scattering, transmission electron microscopy, and atomic force microscopy. It is found that, in water, a solvent selectively good for PEG blocks; these star-block copolymer chains could self-assemble to form platelet-like micelles with insoluble PE blocks as crystalline core and soluble PEG blocks as shell. The confined crystallization of PE blocks in self-assembled structure formed in aqueous solution is investigated by differential scanning calorimetry.

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Section: Introductionmentioning

confidence: 99%

Synthesis and self‐assembly of amphiphilic star‐block copolymers consisting of polyethylene and poly(ethylene glycol) segments

Liu¹,

Li²,

Wang³

et al. 2013

J of Applied Polymer Sci

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show abstract

“…[1][2][3][4][5][6][7][8][9] The coil-brush block copolymers in selective solvents can self-assemble into a variety of regular nanostructures, including spherical, [7,[10][11][12][13] hexagonal, [14] cylindrical, [15,16] vesicle, [17,18] and lamellar morphologies. [19] In order to investigate the self-assembly of coil-brush block copolymer, the preparation of a well-defined block copolymer is crucial.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Self‐Assembly of New Double‐Crystalline Amphiphilic Polyethylene‐block‐Poly[oligo(ethylene glycol) Methyl Ether Methacrylate] Coil‐Brush Diblock Copolymer

Wang

Liu

et al. 2010

Macro Chemistry & Physics

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We report on the synthesis and self-assembly of a novel well-defined coil-brush diblock copolymer with linear crystalline polyethylene (PE) as the coil block and hydrophilic poly [oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) as rod brush via a combination of chain shuttling ethylene polymerization (CSEP) and atom transfer radical polymerization (ATRP). Initially, bromine end-terminated PE macroinitiator (PE-Br) was synthesized through the esterification of 2-bromo-2-methylpropionyl bromide with monohydroxyl-terminated PE (PE-OH) which was prepared by means of CSEP with 2,6-bis[1-(2,6-dimethylphenyl)imino ethyl] pyridine iron (II) dichloride/methylaluminoxane (MAO)/ZnEt 2 and subsequent in situ oxidation with oxygen. The resultant PE-b-POEGMA coil-brush diblock copolymer was synthesized by ATRP of monomethoxy-capped oligo(ethylene glycol)methacrylate (OEGMA) using PE-Br as macroinitiator. The self-assembly of the double-crystalline PE-b-POEGMA in aqueous solution was investigated by dynamic light scattering, transmission electron microscopy and cryofield emission scanning electron microscopy. It was found that, in water, a solvent selectively good for the POEGMA brush, PE-b-POEGMA chains could self-assemble to form sandwich-like micelles with the insoluble and crystallized PE blocks as the interlayer cores and the soluble and swollen POEGMA brush as the outer-layer shell. The crystallization of both PE and POEGMA blocks in self-assembled structure formed from aqueous solution was investigated by differential scanning calorimetry.

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“…The assembly behavior of coil–brush polymers is expected to be fundamentally different from either linear or brush block polymers; the molecular parameters within their unconventional asymmetric architecture are associated with an interesting set of trade-offs between various polymer–polymer/surface/solvent interactions in the system, caused by their intrinsic imbalances. Owing to their molecular geometry, they exhibit distinct microphase separation patterns in the bulk and at interfaces and assemble into defined aggregates in solution. − Among all the characteristics, the ability of amphiphilic coil–brush polymers to self-assemble into numerous nanoscopic objects, including spherical, − ,, hexagonal, cylindrical, , vesicle, lamellar morphologies, etc. , offers significant diversity in the construction of well-defined nanoscopic materials.…”

mentioning

confidence: 99%

Experiments and Simulations of Complex Sugar-Based Coil−Brush Block Polymer Nanoassemblies in Aqueous Solution

et al. 2019

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In this work, we investigated the fundamental molecular parameters that guide the supramolecular assembly of glucose-based amphiphilic coil–brush block polymers in aqueous solution and elucidated architecture–morphology relationships through experimental and simulation tools. Well-defined coil–brush polymers were synthesized through ring-opening polymerizations (ROP) of glucose carbonates to afford norbornenyl-functionalized poly(glucose carbonate) (NB-PGC) macromonomers, followed by sequential ring-opening metathesis polymerizations (ROMP) of norbornene N-hydroxysuccinimidyl (NHS) esters and the NB-PGC macromonomers. Variation of the macromonomer length and grafting through ROMP conditions allowed for a series of coil–brush polymers to be synthesized with differences in the brush and coil dimensions, independently, where the side chain graft length and brush backbone were used to tune the brush, and the coil block length was used to vary the coil. Hydrolysis of the NHS moieties gave the amphiphilic coil–brush polymers, where the hydrophilic–hydrophobic ratios were dependent on the brush and coil relative dimensions. Experimental assembly in solution was studied and found to yield a variety of structurally dependent nanostructures. Simulations were conducted on the solution assembly of coil–brush polymers, where the polymers were represented by a coarse-grained model and the solvent was represented implicitly. There is qualitative agreement in the phase diagrams obtained from simulations and experiments, in terms of the morphologies of the assembled nanoscopic structures achieved as a function of coil–brush design parameters (e.g., brush and coil lengths, composition). The simulations further showed the chain conformations adopted by the coil–brush polymers and the packing within these assembled nanoscopic structures. This work enables the predictive design of nanostructures from this glucose-based coil–brush polymer platform while providing a fundamental understanding of interactions within solution assembly of complex polymer building blocks.

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Architecture of rod–brush block copolymers synthesized by a combination of coordination polymerization and atom transfer radical polymerization

Cited by 4 publications

References 25 publications

Synthesis and self‐assembly of amphiphilic star‐block copolymers consisting of polyethylene and poly(ethylene glycol) segments

Synthesis and self‐assembly of amphiphilic star‐block copolymers consisting of polyethylene and poly(ethylene glycol) segments

Synthesis and Self‐Assembly of New Double‐Crystalline Amphiphilic Polyethylene‐block‐Poly[oligo(ethylene glycol) Methyl Ether Methacrylate] Coil‐Brush Diblock Copolymer

Experiments and Simulations of Complex Sugar-Based Coil−Brush Block Polymer Nanoassemblies in Aqueous Solution

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