Well-Defined Amphiphilic Double-Brush Copolymers and Their Performance as Emulsion Surfactants

Li, Yukun; Zou, Jiong; Das, Biswa P.; Tsianou, Marina; Cheng, Chong

doi:10.1021/ma300565j

Cited by 101 publications

(131 citation statements)

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“…11B). DBCs with hetero-grafted PEO and PLA side-chains were added to a water/toluene mixture and found to stabilize mini-emulsion droplets 127 . Zhang et al synthesized core-shell bottlebrush polymers using a grafting-onto synthesis 129 .…”

Section: Non-associating Bottlebrushes For Encapsulation and Deliverymentioning

confidence: 99%

Structure, function, self-assembly, and applications of bottlebrush copolymers

et al. 2015

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Bottlebrush polymers are a type of branched or graft polymer with polymeric side-chains attached to a linear backbone, and the unusual architecture of bottlebrushes provides a number of unique and potentially useful properties. These include a high entanglement molecular weight, enabling rapid self-assembly of bottlebrush block copolymers into large domain structures, the self-assembly of bottlebrush block copolymer micelles in a selective solvent even at very low dilutions, and the functionalization of bottlebrush side-chains for recognition, imaging, or drug 2 delivery in aqueous environments. This review article focuses on recent developments in the field of bottlebrush polymers with an emphasis on applications of bottlebrush copolymers.Bottlebrush copolymers contain two (or more) different types of polymeric side-chains. Recent work has explored the diverse properties and functions of bottlebrush polymers and copolymers in solutions, films, and melts, and applications explored include photonic materials, bottlebrush films for lithographic patterning, drug delivery, and tumor detection and imaging. We provide a brief introduction to bottlebrush synthesis and physical properties and then discuss work related to: i) bottlebrush self-assembly in melts and bulk thin films, ii) bottlebrushes for photonics and lithography, iii) bottlebrushes for small molecule encapsulation and delivery in solution, and iv) bottlebrush micelles and assemblies in solution. We briefly discuss three potential areas for future research, including developing a more quantitative model of bottlebrush self-assembly in the bulk, studying the properties of bottlebrushes at interfaces, and investigating the solution assembly of bottlebrush copolymers.

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Section: Non-associating Bottlebrushes For Encapsulation and Deliverymentioning

confidence: 99%

Structure, function, self-assembly, and applications of bottlebrush copolymers

et al. 2015

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“…1,3,4 Even if we consider only the ones prepared using ROMP of MMs, brush (co)-polymers have already been widely used as soft photonic crystals, 8,21,27 drug delivery vehicles, 28−32 optoelectronic and lithographic materials, 22,33,34 and surface or rheological modifiers. 14,35,36 Synthesis of monofunctional MMs is a critical step toward successful synthesis of brush polymers via ROMP. Two methods can be used to prepare MMs: (1) direct growth from a norbornenyl-functionalized initiator or chain transfer agent (CTA), which we annotate as "direct-growth" MM (DG-MM), and (2) premade polymer end-capped or coupled to a norbornenyl group, which we annotate as "growth-thencoupling" MM (GC-MM) ( Figure 1).…”

Section: ■ Introductionmentioning

confidence: 99%

Importance of Macromonomer Quality in the Ring-Opening Metathesis Polymerization of Macromonomers

Teo

Xia

2015

Macromolecules

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Various macromonomers (MMs) were synthesized using controlled radical polymerization (CRP) by either directly growing from a norbornene-functionalized initiator or chain transfer agent ("direct-growth" or DG method) or coupling a norbornenyl group to preformed polymers ("growth-then-coupling" or GC method). The degree of control for the ring-opening metathesis polymerization (ROMP) of these MMs was found to be dependent on which synthetic method was used for the MMs. Narrowly dispersed brush polymers were consistently obtained from the GC-MMs. In contrast, the DG-MMs resulted in brush polymers with a small high-molecular weight (MW) shoulder or broader molecular weight distribution (MWD). Matrix-assisted laser desorption ionization time-of-flight mass spectrometry of DG-MMs showed the presence of a small amount of α,ω-dinorbornenyl telechelic species resulting from the biradical combination during polymerization. A control study further revealed that even the presence of 1 mol % α,ω-norbornenyl telechelic polymer in the MM resulted in broadening of MWD. Our surprising findings suggest the importance of MM quality and the absence of dinorbornenyl telechelic polymers in achieving the best control for high-MW brush polymers via efficient ROMP of MMs.

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“…The enhanced steric repulsion between the densely grafted side chains forces the main chains to elongate. They were successfully synthesized via several grafting strategies, including "graft-through" [6][7][8][9][10][17][18][19][20] , "graft-from" 4,5,12,13,21,22 , "graft-to" [23][24][25] , as well as their varied combinations 26 , which have been summarized in recent reviews 2,3 . During the past decades, polymer molecular brushes have received progressively growing attention.…”

Section: Introductionmentioning

confidence: 99%

Efficient synthesis of narrowly dispersed amphiphilic double-brush copolymers through the polymerization reaction of macromonomer micelle emulsifiers at the oil–water interface

Han

Gao

et al. 2016

Polym. Chem.

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In this study, well-defined amphiphilic double-brush copolymers (DBCs) with narrow molecular weight distributions were efficiently synthesized by radical polymerization of macromonomers directed by Pickering emulsion template at oil-water interface.Firstly, well-defined poly(methyl methacrylate)-b-poly(N,N-dimethyl acryamide) (PMMA-b-PDMA) diblock macromonomer carrying a pendent methacryloyl (MA) group at the block junction (MA-PMMA-b-PDMA) was synthesized through sequential atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization, followed by an acrylation functionalization reaction. The MA-PMMA-b-PDMA macromonomer could self-assemble into core-shell micelles with hydrophobic PMMA-based cores, hydrophilic PDMA shells and MA groups at core-shell boundary. The as-formed core-shell micelles were then employed as emulsifiers for the formation of stabilized oil-in-water (o/w) Pickering emulsion, in which the macromonomer micelles were locked at the oil-water interface and presented Janus-like conformation. At last, the conventional radical polymerization reaction was carried out for the MA groups of the macromonomer micelles absorbed at the oil-water interface using azobiisobutyronitrile (AIBN) pre-encapsulated in the Pickering emulsion oil droplets as initiator, leading to well-defined PMA-g-PMMA/PDMA DBCs with narrow molecular weight distributions. The as-formed DBCs showed higher degrees of polymerization of backbones than the DBCs synthesized by micellar polymerization of the macromonomer in pure water, presumably due to the facilitated propagation reaction between the neighboring micelles in the former cases. The macromonomers and DBCs were carefully characterized by various instrumental analytical techniques. displayed the 1 H NMR spectra of BEMP and BMBP. For BEMP, the respective resonances were clearly assigned, which were in good agreement with the early reports 40 . Different with the 1 H NMR spectrum of BEMP, the spectrum of BMBP showed new resonances at 4.15-4.07 and 1.94 ppm. These resonances were assigned to the methylene protons of -C(Br)COOCH 2 group and the methyl protons of -C(Br)CH 3 group, respectively. The 1 H NMR results confirmed that the designed BMBP was successfully synthesized. Scheme 2. Synthesis routes of BEMP, BMBP, PMMA, PMMA-b-PDMA, MA-PMMA-b-PDMA, and PMA-g-PMMA/PDMA. (i) EMP/DCC/DMAP/acetone, room temperature; (ii) 2-bromoisobutyryl bromide/Et 3 N/CH 2 Cl 2 , room temperature; (iii) MMA/CuBr/PMDETA/anisole; (iv) DMA/AIBN/DMF; (v) methacryloyl chloride,Et 3 N/CH 2 Cl 2 ; (vi) AIBN/70 ℃.Fig. 4 (A) Volume-average distribution of the hydrodynamic diameters of macromonomer micelles in water; (B) TEM image of macromonomer micelles without staining; (C,D) TEM images of macromonomer micelles stained by phosphotungstic acid solution. Core crosslinked star-like (CCS) polymer nanoparticles exhibited excellent emulsifying performances, and can allow for the generation of highly stabilized Pickering emulsions at extremely low contents ...

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Well-Defined Amphiphilic Double-Brush Copolymers and Their Performance as Emulsion Surfactants

Cited by 101 publications

References 44 publications

Structure, function, self-assembly, and applications of bottlebrush copolymers

Structure, function, self-assembly, and applications of bottlebrush copolymers

Importance of Macromonomer Quality in the Ring-Opening Metathesis Polymerization of Macromonomers

Efficient synthesis of narrowly dispersed amphiphilic double-brush copolymers through the polymerization reaction of macromonomer micelle emulsifiers at the oil–water interface

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