ROMP-Derived Pyridylborate Block Copolymers: Self-Assembly, pH-Responsive Properties, and Metal-Containing Nanostructures

Gajanan M. Pawar, Roger Lalancette, Edward Bonder, John B. Sheridan, Frieder Jaekle

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The functionalization of organic polymers with polydentate ligands offers opportunities in areas ranging from supported catalysts to materials with desirable magnetic, redox-active, stimuli-responsive, and self-healing properties. Herein, we present the synthesis and self-assembly of tris(2-pyridyl)borate (Tpyb)-functionalized homo and block copolymers, prepared via ring-opening metathesis polymerization (ROMP) of (bicyclo[2.2.1]hept-5-en-2-yl)-4-phenyl) (pyridin-1-ium-2-yl)di(pyridin-2-yl)borate (M1) and dimethyl-7-oxabicyclo[2.2.1]hept-5-ene-exo,exo-2,3-dicarboxylate (M2) using Grubbs third-generation catalyst. Controlled polymerization was confirmed by gel permeation chromatography (GPC; also referred to as size exclusion chromatography, SEC) and multinuclear NMR spectroscopy. The solution self-assembly in block-selective solvents (MeOH, THF) was investigated by dynamic light scattering (DLS), scanning electron microscopy (SEM), scanning tunneling electron microscopy (STEM), and transmission electron microscopy (TEM), and the microphase separation in a thin film was imaged by atomic force microscopy (AFM). Hydrolysis of the ester-substituted oxanorbornene block with NaOH led to a new copolymer with carboxylate functionalities that can be dispersed in water. The latter displays multiresponsive properties as each of the individual blocks can be reversibly switched between hydrophobic and hydrophilic states by simple adjustment of pH. Cross-linking of the block copolymer aggregates via metal ion complexation was accomplished, and the feasibility of metal ion exchange was demonstrated by energy-dispersive X-ray spectroscopy (EDX).

Original languageEnglish (US)
Pages (from-to)6508-6515
Number of pages8
JournalMacromolecules
Volume48
Issue number18
DOIs
StatePublished - Sep 22 2015

Fingerprint

Borates
Ring opening polymerization
Self assembly
Block copolymers
Metal ions
Nanostructures
Metals
Microphase separation
Organic polymers
Size exclusion chromatography
Gel permeation chromatography
Scanning tunneling microscopy
Dynamic light scattering
Complexation
Catalyst supports
Electron microscopy
Nuclear magnetic resonance spectroscopy
Hydrolysis
Atomic force microscopy
Ion exchange

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

@article{b7370ef2932449b08c301a4791be28e5,
title = "ROMP-Derived Pyridylborate Block Copolymers: Self-Assembly, pH-Responsive Properties, and Metal-Containing Nanostructures",
abstract = "The functionalization of organic polymers with polydentate ligands offers opportunities in areas ranging from supported catalysts to materials with desirable magnetic, redox-active, stimuli-responsive, and self-healing properties. Herein, we present the synthesis and self-assembly of tris(2-pyridyl)borate (Tpyb)-functionalized homo and block copolymers, prepared via ring-opening metathesis polymerization (ROMP) of (bicyclo[2.2.1]hept-5-en-2-yl)-4-phenyl) (pyridin-1-ium-2-yl)di(pyridin-2-yl)borate (M1) and dimethyl-7-oxabicyclo[2.2.1]hept-5-ene-exo,exo-2,3-dicarboxylate (M2) using Grubbs third-generation catalyst. Controlled polymerization was confirmed by gel permeation chromatography (GPC; also referred to as size exclusion chromatography, SEC) and multinuclear NMR spectroscopy. The solution self-assembly in block-selective solvents (MeOH, THF) was investigated by dynamic light scattering (DLS), scanning electron microscopy (SEM), scanning tunneling electron microscopy (STEM), and transmission electron microscopy (TEM), and the microphase separation in a thin film was imaged by atomic force microscopy (AFM). Hydrolysis of the ester-substituted oxanorbornene block with NaOH led to a new copolymer with carboxylate functionalities that can be dispersed in water. The latter displays multiresponsive properties as each of the individual blocks can be reversibly switched between hydrophobic and hydrophilic states by simple adjustment of pH. Cross-linking of the block copolymer aggregates via metal ion complexation was accomplished, and the feasibility of metal ion exchange was demonstrated by energy-dispersive X-ray spectroscopy (EDX).",
author = "Pawar, {Gajanan M.} and Roger Lalancette and Edward Bonder and Sheridan, {John B.} and Frieder Jaekle",
year = "2015",
month = "9",
day = "22",
doi = "10.1021/acs.macromol.5b01216",
language = "English (US)",
volume = "48",
pages = "6508--6515",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "18",

}

ROMP-Derived Pyridylborate Block Copolymers : Self-Assembly, pH-Responsive Properties, and Metal-Containing Nanostructures. / Pawar, Gajanan M.; Lalancette, Roger; Bonder, Edward; Sheridan, John B.; Jaekle, Frieder.

In: Macromolecules, Vol. 48, No. 18, 22.09.2015, p. 6508-6515.

Research output: Contribution to journalArticle

TY - JOUR

T1 - ROMP-Derived Pyridylborate Block Copolymers

T2 - Self-Assembly, pH-Responsive Properties, and Metal-Containing Nanostructures

AU - Pawar, Gajanan M.

AU - Lalancette, Roger

AU - Bonder, Edward

AU - Sheridan, John B.

AU - Jaekle, Frieder

PY - 2015/9/22

Y1 - 2015/9/22

N2 - The functionalization of organic polymers with polydentate ligands offers opportunities in areas ranging from supported catalysts to materials with desirable magnetic, redox-active, stimuli-responsive, and self-healing properties. Herein, we present the synthesis and self-assembly of tris(2-pyridyl)borate (Tpyb)-functionalized homo and block copolymers, prepared via ring-opening metathesis polymerization (ROMP) of (bicyclo[2.2.1]hept-5-en-2-yl)-4-phenyl) (pyridin-1-ium-2-yl)di(pyridin-2-yl)borate (M1) and dimethyl-7-oxabicyclo[2.2.1]hept-5-ene-exo,exo-2,3-dicarboxylate (M2) using Grubbs third-generation catalyst. Controlled polymerization was confirmed by gel permeation chromatography (GPC; also referred to as size exclusion chromatography, SEC) and multinuclear NMR spectroscopy. The solution self-assembly in block-selective solvents (MeOH, THF) was investigated by dynamic light scattering (DLS), scanning electron microscopy (SEM), scanning tunneling electron microscopy (STEM), and transmission electron microscopy (TEM), and the microphase separation in a thin film was imaged by atomic force microscopy (AFM). Hydrolysis of the ester-substituted oxanorbornene block with NaOH led to a new copolymer with carboxylate functionalities that can be dispersed in water. The latter displays multiresponsive properties as each of the individual blocks can be reversibly switched between hydrophobic and hydrophilic states by simple adjustment of pH. Cross-linking of the block copolymer aggregates via metal ion complexation was accomplished, and the feasibility of metal ion exchange was demonstrated by energy-dispersive X-ray spectroscopy (EDX).

AB - The functionalization of organic polymers with polydentate ligands offers opportunities in areas ranging from supported catalysts to materials with desirable magnetic, redox-active, stimuli-responsive, and self-healing properties. Herein, we present the synthesis and self-assembly of tris(2-pyridyl)borate (Tpyb)-functionalized homo and block copolymers, prepared via ring-opening metathesis polymerization (ROMP) of (bicyclo[2.2.1]hept-5-en-2-yl)-4-phenyl) (pyridin-1-ium-2-yl)di(pyridin-2-yl)borate (M1) and dimethyl-7-oxabicyclo[2.2.1]hept-5-ene-exo,exo-2,3-dicarboxylate (M2) using Grubbs third-generation catalyst. Controlled polymerization was confirmed by gel permeation chromatography (GPC; also referred to as size exclusion chromatography, SEC) and multinuclear NMR spectroscopy. The solution self-assembly in block-selective solvents (MeOH, THF) was investigated by dynamic light scattering (DLS), scanning electron microscopy (SEM), scanning tunneling electron microscopy (STEM), and transmission electron microscopy (TEM), and the microphase separation in a thin film was imaged by atomic force microscopy (AFM). Hydrolysis of the ester-substituted oxanorbornene block with NaOH led to a new copolymer with carboxylate functionalities that can be dispersed in water. The latter displays multiresponsive properties as each of the individual blocks can be reversibly switched between hydrophobic and hydrophilic states by simple adjustment of pH. Cross-linking of the block copolymer aggregates via metal ion complexation was accomplished, and the feasibility of metal ion exchange was demonstrated by energy-dispersive X-ray spectroscopy (EDX).

UR - http://www.scopus.com/inward/record.url?scp=84942288029&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84942288029&partnerID=8YFLogxK

U2 - 10.1021/acs.macromol.5b01216

DO - 10.1021/acs.macromol.5b01216

M3 - Article

AN - SCOPUS:84942288029

VL - 48

SP - 6508

EP - 6515

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 18

ER -