Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Dynamic Control over Aqueous Poly(butadiene-b-ethylene oxide) Self-Assembly through Olefin Metathesis

Journal Article · · Macromolecules

Here, we show that olefin metathesis can be used in an extremely simple process to rapidly alter the morphology of self-assembled poly(butadiene-b-ethylene oxide) (PB–PEO) dispersions in situ. The addition of a water-insoluble Hoveyda–Grubbs catalyst to aqueous assemblies of PB–PEO leads to degradation of the hydrophobic PB block by well-established metathesis pathways and a concomitant change in the composition of the block copolymer. This phenomenon drives morphological transitions characterized by rapidly decreasing sizes of the self-assembled aggregates, the ultimate extent of which is readily controlled by catalyst concentration. Exemplary cases are presented in which transitions from worm-like micelles to spherical micelles or from vesicles to worm-like micelles can be accomplished within minutes.

Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1465387
Alternate ID(s):
OSTI ID: 1479020
OSTI ID: 1484666
Report Number(s):
SAND--2018-8649J; 666957
Journal Information:
Macromolecules, Journal Name: Macromolecules Journal Issue: 17 Vol. 51; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (46)

Quantitative description of the metathesis polymerization/depolymerization equilibrium in the 1,4-polybutadiene system, 1. Influence of feed concentration and temperature journal July 1999
Controlled Chain-Scission of Polybutadiene by the Schwartz Hydrozirconation journal November 2012
Anwendung der Metathese-Reaktion auf die Mikrostrukturbestimmung von Polybutadienen journal March 1975
Sequenzlängenverteilungsanalyse der 1,2-Einheiten in Polybutadienen an Hand der Olefin-Polymeres/Metathese-Reaktion; ein Weg zur Darstellung von mono- und disubstituierten Cyclopenten- wie auch Cyclohexen-Verbindungen journal April 1979
Metathetic Selective Degradation of Polyisoprene: Low-Molecular-Weight Telechelic Oligomer Obtained from Both Synthetic and Natural Rubber journal May 2005
Acyclic diene metathesis (ADMET) depolymerization: The synthesis of 1,4-polybutadiene telechelics journal August 1995
CONTIN: A general purpose constrained regularization program for inverting noisy linear algebraic and integral equations journal September 1982
Micellization of block copolymers journal July 2003
Block copolymer micelles: preparation, characterization and application in drug delivery journal December 2005
The metathetic degradation of polyisoprene and polybutadiene in block copolymers using Grubbs second generation catalyst journal June 2011
Single-phase block copolymers by cross-metathesis of 1,4-cis-polybutadiene and 1,4-cis-polyisoprene journal November 2017
Recent advances and challenges in designing stimuli-responsive polymers journal January 2010
A Critical Appraisal of RAFT-Mediated Polymerization-Induced Self-Assembly journal March 2016
PEE–PEO Block Copolymer Exchange Rate between Mixed Micelles Is Detergent and Temperature Activated journal March 2017
Exchange Kinetics for a Single Block Copolymer in Micelles of Two Different Sizes journal March 2018
ROMPISA: Ring-Opening Metathesis Polymerization-Induced Self-Assembly journal August 2017
Aqueous-Phase Ring-Opening Metathesis Polymerization-Induced Self-Assembly journal March 2018
Mechanistic Insights for Block Copolymer Morphologies: How Do Worms Form Vesicles? journal October 2011
Making Insoluble Polymer Networks Malleable via Olefin Metathesis journal May 2012
One-Pot in Situ Fabrication of Stable Nanocaterpillars Directly from Polyacetylene Diblock Copolymers Synthesized by Mild Ring-Opening Metathesis Polymerization journal August 2012
Janus Micelles Induced by Olefin Metathesis journal May 2008
Quantitative Ring-Closing Metathesis of Polyolefins journal January 1996
Multiple Morphologies and Characteristics of “Crew-Cut” Micelle-like Aggregates of Polystyrene- b -poly(acrylic acid) Diblock Copolymers in Aqueous Solutions journal January 1996
Control of the Morphology of Linear and Cyclic PS- b -PI Block Copolymer Micelles via PS Addition journal February 2005
Metathesis Depolymerization for Removable Surfactant Templates journal September 2005
Preparation of Monodisperse Block Copolymer Vesicles via a Thermotropic Cylinder−Vesicle Transition journal January 2009
Acyclic diene metathesis (ADMET) depolymerization. Synthesis of mass-exact telechelic polybutadiene oligomers journal April 1993
ADMET Depolymerization. Synthesis of Perfectly Difunctional (f = 2.0) Telechelic Polybutadiene Oligomers journal April 1995
Multicompartment Block Polymer Micelles journal December 2011
Predictive Phase Diagrams for RAFT Aqueous Dispersion Polymerization: Effect of Block Copolymer Composition, Molecular Weight, and Copolymer Concentration journal June 2012
Exchange of Polymer Molecules between Block Copolymer Micelles Studied by Emission Spectroscopy. A Method for the Quantification of Unimer Exchange Rates journal July 1997
Evolution of Block Copolymer Micellar Size and Structure Evidenced with Cryo Electron Microscopy journal May 1998
Solvent-Free Olefin Metathesis Depolymerization of 1,4-Polybutadiene journal March 2000
Dynamic instability of microtubule growth journal November 1984
Single-cell dynamics of the chromosome replication and cell division cycles in mycobacteria journal September 2013
Size evolution of highly amphiphilic macromolecular solution assemblies via a distinct bimodal pathway journal April 2014
Controlled polymer synthesis—from biomimicry towards synthetic biology journal January 2010
Thermally induced micelle to vesicle morphology transition for a charged chain end diblock copolymer journal January 2010
Dispersity effects in polymer self-assemblies: a matter of hierarchical control journal January 2017
Stimuli-responsive polymersomes and nanoreactors journal January 2016
Olefin cross metathesis and ring-closing metathesis in polymer chemistry journal January 2017
Mechanism of Molecular Exchange in Diblock Copolymer Micelles: Hypersensitivity to Core Chain Length journal January 2010
Logarithmic Chain-Exchange Kinetics of Diblock Copolymer Micelles journal February 2006
Polymer Vesicles journal August 2002
On the Origins of Morphological Complexity in Block Copolymer Surfactants journal April 2003
Worm-like micelles in water solutions of 1, 4 poly (1, 3-butadiene)-polyethylene oxide diblock copolymer journal June 2014

Cited By (2)

Functionalization-induced self-assembly under ambient conditions via thiol-epoxide “click” chemistry journal January 2020
Sphere-to-worm morphological transitions and size changes through thiol– para -fluoro core modification of PISA-made nano-objects journal January 2020

Similar Records

Depolymerization of Cross-Linked Polybutadiene Networks in Situ Using Latent Alkene Metathesis
Journal Article · Wed Jul 24 00:00:00 EDT 2019 · ACS Applied Polymer Materials · OSTI ID:1559496

Lyotropic Phase Behavior of Poly(ethylene oxide)-Poly(butadiene) Diblock Copolymers: Evolution of the Random Network Morphology
Journal Article · Fri Oct 24 00:00:00 EDT 2008 · Macromolecules · OSTI ID:1006691

FT-IR Investigation of Hoveyda-Grubbs'2{sup nd} Generation Catalyst in Self-Healing Epoxy Mixtures
Journal Article · Wed Jun 02 00:00:00 EDT 2010 · AIP Conference Proceedings · OSTI ID:21377992