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Control of polymer architectures by living ring-opening metathesis copolymerization

Patent ·
OSTI ID:1840227

In an aspect, a method of synthesizing a graft copolymer comprises the steps of: copolymerizing a first macromonomer and a first reactive diluent; wherein said first macromonomer comprises a first backbone precursor directly or indirectly covalently linked to a first polymer side chain group; wherein said reactive diluent is provided in the presence of the first macromonomer at an amount selected so as to result in formation said graft copolymer having a first backbone incorporating said diluent and said first macromonomer in a first polymer block characterized by a preselected first graft density or a preselected first graft distribution of said first macromonomer. In some embodiments of this aspect, said preselected first graft density is any value selected from the range of 0.05 to 0.75. In some methods, the composition and amount of said diluent is selected to provide both a first preselected first graft density and a first preselected first graft distribution.

Research Organization:
California Inst. of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Organization:
USDOE; National Science Foundation (NSF)
DOE Contract Number:
AR0000683
Assignee:
California Institute of Technology (Pasadena, CA)
Patent Number(s):
11,053,356
Application Number:
15/914,762
OSTI ID:
1840227
Country of Publication:
United States
Language:
English

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Mechanisms Underlying Ion Transport in Lamellar Block Copolymer Membranes journal March 2012
Molecular Bottlebrushes: New Opportunities in Nanomaterials Fabrication journal September 2012
Molecular Weight Dependence of Zero-Shear Viscosity in Atactic Polypropylene Bottlebrush Polymers journal April 2014
Molecular Design of Liquid Crystalline Brush-Like Block Copolymers for Magnetic Field Directed Self-Assembly: A Platform for Functional Materials journal April 2014
Facile One-Pot Synthesis of Brush Polymers through Tandem Catalysis Using Grubbs' Catalyst for Both Ring-Opening Metathesis and Atom Transfer Radical Polymerizations journal July 2006
High-Modulus, High-Conductivity Nanostructured Polymer Electrolyte Membranes via Polymerization-Induced Phase Separation journal December 2013
Effect of Ion Distribution on Conductivity of Block Copolymer Electrolytes journal March 2009
Oligosaccharide/Silicon-Containing Block Copolymers with 5 nm Features for Lithographic Applications journal March 2012
Cyclic Block Copolymers for Controlling Feature Sizes in Block Copolymer Lithography journal November 2012
Self-Assembly of Symmetric Brush Diblock Copolymers journal February 2013
On the Self-Assembly of Brush Block Copolymers in Thin Films journal October 2013
Intramolecular Hydroamination of Aminoalkynes with Silver−Phenanthroline Catalysts journal September 2008
Study Concerning the Effects of Chelation on the Structure and Catalytic Activity of Ruthenium Carbene Complexes journal January 2002
Structural and Mechanistic Basis of the Fast Metathesis Initiation by a Six-Coordinated Ruthenium Catalyst journal June 2013
Conformational Analysis of Olefin−Carbene Ruthenium Metathesis Catalysts journal April 2009
Safe and Convenient Procedure for Solvent Purification journal January 1996
Removal of Palladium from Organic Reaction Mixtures by Trimercaptotriazine journal July 1997
A three-dimensional photonic crystal operating at infrared wavelengths journal July 1998
Phase behaviour of concentrated suspensions of nearly hard colloidal spheres journal March 1986
Fabrication of photonic crystals for the visible spectrum by holographic lithography journal March 2000
Hierarchical self-assembly of metal nanostructures on diblock copolymer scaffolds journal December 2001
Microporous materials: Electrochemically grown photonic crystals journal December 1999
Impact of urbanization and land-use change on climate journal May 2003
Impact of regional climate change on human health journal November 2005
Nanostructured functional materials prepared by atom transfer radical polymerization journal June 2009
Self-assembled polymeric solid films with temperature-induced large and reversible photonic-bandgap switching journal November 2004
Broad-wavelength-range chemically tunable block-copolymer photonic gels journal October 2007
Printable ion-gel gate dielectrics for low-voltage polymer thin-film transistors on plastic journal October 2008
Ionic-liquid materials for the electrochemical challenges of the future journal July 2009
Plasmonics for improved photovoltaic devices journal February 2010
Solvent-free, supersoft and superelastic bottlebrush melts and networks journal November 2015
Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials journal October 2010
Ionic Liquid Co-catalyzed Artificial Photosynthesis of CO journal January 2013
Electrocatalytic and homogeneous approaches to conversion of CO 2 to liquid fuels journal January 2009
Molecular approaches to the electrochemical reduction of carbon dioxide journal January 2012
Catalysis of the electrochemical reduction of carbon dioxide journal January 2013
Ionic liquid polymer electrolytes journal January 2013
Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO) 3 Cl (bipy = 2,2′-bipyridine) journal January 1984
One- and two-electron pathways in the electrocatalytic reduction of CO 2 by fac-Re(bpy)(CO) 3 Cl (bpy = 2,2′-bipyridine) journal January 1985
Reactivity of a fac-ReCl(α-diimine)(CO) 3 complex with an NAD + model ligand toward CO 2 reduction journal January 2014
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels journal January 2014
Energy applications of ionic liquids journal January 2014
A local proton source in a [Mn(bpy-R)(CO) 3 Br]-type redox catalyst enables CO 2 reduction even in the absence of Brønsted acids journal January 2014
Electrocatalytic CO 2 reduction with a membrane supported manganese catalyst in aqueous solution journal January 2014
Towards a methanol economy based on homogeneous catalysis: methanol to H 2 and CO 2 to methanol journal January 2015
Structure, function, self-assembly, and applications of bottlebrush copolymers journal January 2015
Electrocatalytic reduction of carbon dioxide on a cobalt tetrakis(4-aminophenyl)porphyrin modified electrode in BMImBF 4 journal January 2014
Synthesis of bottlebrush polymers via transfer-to and grafting-through approaches using a RAFT chain transfer agent with a ROMP-active Z-group journal January 2015
Controlled ionic conductivity via tapered block polymer electrolytes journal January 2015
Precision polymers: a kinetic approach for functional poly(norbornenes) journal January 2014
A robust and efficient cobalt molecular catalyst for CO 2 reduction journal January 2015
Nanocomposite hydrogels based on liquid crystalline brush-like block copolymer–Au nanorods and their application in H2O2 detection journal January 2015
Ionic liquids enhance the electrochemical CO 2 reduction catalyzed by MoO 2 journal January 2015
CO2 separation, capture and reuse: a web themed issue journal January 2015
Biodegradation of ionic liquids – a critical review journal January 2015
Ionic liquids in the electrochemical valorisation of CO 2 journal January 2015
Synthesis and evaluation of cationic norbornanes as peptidomimetic antibacterial agents journal January 2015
Microphase separation of short wormlike diblock copolymers with a finite interaction range journal January 2016
Synthesis of sequence-determined bottlebrush polymers based on sequence determination in living anionic copolymerization of styrene and dimethyl(4-(1-phenylvinyl)phenyl)silane journal January 2016
Theoretical simulations of nanostructures self-assembled from copolymer systems journal January 2016
Alternating ring-opening metathesis copolymerization of bicyclo[2.2.1]hept-2-ene and cyclopentene journal January 1997
Coarse-grained simulations of ABA amphiphilic triblock copolymer solutions in thin films journal January 2007
Manipulating ordering transitions in interfacially modified block copolymers journal January 2009
Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives journal January 2011
Continuously tuneable optical filters from self-assembled block copolymer blends journal January 2011
Volatilisation of ferrocene from ionic liquids: kinetics and mechanism journal January 2011
Photocatalytic reduction of CO2: a brief review on product analysis and systematic methods journal January 2013
Helical polymer brushes with a preferred-handed helix-sense triggered by a terminal optically active group in the pendant journal January 2012
Structural investigations into the deactivation pathway of the CO2 reduction electrocatalyst Re(bpy)(CO)3Cl journal January 2012
Self-assembly of block copolymers journal January 2012
Smart polymer brushes and their emerging applications journal January 2012
High CO2 solubility, permeability and selectivity in ionic liquids with the tetracyanoborate anion journal January 2012
Electrocatalytic reduction of CO2 at a chemically modified electrode journal January 1985
Direct observation of the reduction of carbon dioxide by rhenium bipyridine catalysts journal January 2013
Ring-opening metathesis polymerization of 8-membered cyclic olefins journal January 2014
Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter journal January 2014
Highly conductive, crosslinked ionomers based on poly(styrene-co-maleic anhydride) for water electrolysis journal January 2013
Molecular rheology of branched polymers: decoding and exploring the role of architectural dispersity through a synergy of anionic synthesis, interaction chromatography, rheometry and modeling journal January 2014
Static and dynamic properties of two-dimensional polymer melts journal January 1990
Patterned polymer growth on silicon surfaces using microcontact printing and surface-initiated polymerization journal December 1999
Dense arrays of ordered GaAs nanostructures by selective area growth on substrates patterned by block copolymer lithography journal March 2000
Integration of self-assembled diblock copolymers for semiconductor capacitor fabrication journal July 2001
Size and persistence length of molecular bottle-brushes by Monte Carlo simulations journal April 2004
On the shape of bottle-brush macromolecules: Systematic variation of architectural parameters journal March 2005
Self-aligned self assembly of multi-nanowire silicon field effect transistors journal October 2005
Physical Properties of Ionic Liquids: Database and Evaluation journal December 2006
Aluminum nanowire polarizing grids: Fabrication and analysis journal May 2006
Plasmonic nanocavity arrays for enhanced efficiency in organic photovoltaic cells journal September 2008
Interdiffusion and self‐diffusion in polymer mixtures: A Monte Carlo study journal February 1991
Melts of semiflexible diblock copolymer journal May 1996
Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity journal January 2015
Block Copolymers—Designer Soft Materials journal February 1999
Fabricating complex three-dimensional nanostructures with high-resolution conformable phase masks journal August 2004
Splitting CO2 into CO and O2 by a single catalyst journal June 2012
Rapid self-assembly of brush block copolymers to photonic crystals journal August 2012
Manipulating the ABCs of self-assembly via low-χ block polymer design journal June 2017
Tube theory of entangled polymer dynamics journal September 2002
Analysis of the Linear Methods for Determining Copolymerization Reactivity Ratios. I. A New Improved Linear Graphic Method journal January 1975
Reactivity of Macromonomers in free Radical Polymerization journal August 1990
Diels-Alder reactions in the presence of a minimal amount of water journal September 2008
Massively parallel fabrication of repetitive nanostructures: nanolithography for nanoarrays journal June 2009
Nanostructure fabrication using block copolymers journal September 2003
⅔ -Power Law for Copolymer Lamellar Thickness Implies a ⅓ -Power Law for Spinodal Decomposition journal August 1988
Thickness Dependence of the Optical Properties of Ordered Silica-Air and Air-Polymer Photonic Crystals journal July 1999
Determination of size distribution from small-angle scattering data for systems with effective hard-sphere interactions journal August 1994
Block copolymers as photonic bandgap materials journal November 1999
Nonlinear rheology of model comb polymers journal September 2009
Molecular structure of bottlebrush polymers in melts journal November 2016
Modern Global Climate Change journal December 2003
Global Change and the Ecology of Cities journal February 2008
MATERIALS SCIENCE: A Unique Platform for Materials Design journal July 2008
Macroscopic 10-Terabit-per-Square-Inch Arrays from Block Copolymers with Lateral Order journal February 2009
Linking Models of Polymerization and Dynamics to Predict Branched Polymer Structure and Flow journal September 2011
Architecturally Complex Polymers with Controlled Heterogeneity journal August 2011
Predicting the Flow of Real Polymers journal September 2011
Multiblock Polymers: Panacea or Pandora's Box? journal April 2012
A Local Proton Source Enhances CO 2 Electroreduction to CO by a Molecular Fe Catalyst journal October 2012
Sequence-Controlled Polymers journal August 2013
Block Copolymer Lithography: Periodic Arrays of 1011 Holes in 1 Square Centimeter journal May 1997
Ultrahigh-Density Nanowire Arrays Grown in Self-Assembled Diblock Copolymer Templates journal December 2000
Photonic Crystal Using Anodic Porous Alumina journal December 1999
Controlling Order in Block Copolymer Thin Films for Nanopatterning Applications journal June 2010
Polymer Electrolytes journal July 2013
Dynamics of Block Copolymers: Theory and Experiment journal August 1996
Block Copolymer Thermodynamics: Theory and Experiment journal October 1990
Electrochemical Intercalation of  PF 6 into Graphite journal January 2000
All Solid-State Lithium-Polymer Battery Using a Self-Cross-Linking Polymer Electrolyte journal January 2003
Rubbery Graft Copolymer Electrolytes for Solid-State, Thin-Film Lithium Batteries journal January 2005
Ionic Liquid‐Polymer Gel Electrolytes journal April 1997
Synthesis of Li[sup +] Ion Conductive PEO-PSt Block Copolymer Electrolyte with Microphase Separation Structure journal January 2005
Synthesis and Characterization of Single-Ion Graft Copolymer Electrolytes journal January 2005
Star-Shaped Polymer Electrolyte with Microphase Separation Structure for All-Solid-State Lithium Batteries journal January 2009
The Selective Electrochemical Conversion of Preactivated CO2to Methane journal January 2015
Transfer-matrix formalism for the calculation of optical response in multilayer systems: from coherent to incoherent interference journal January 2010
Block Copolymer Lithography: Merging “Bottom-Up” with “Top-Down” Processes journal December 2005
Self-Assembly of Block Copolymers for Photonic-Bandgap Materials journal October 2005
Block Copolymer Nanostructures for Technology journal October 2010
From Self-Assembled Monolayers to Coatings: Advances in the Synthesis and Nanobio Applications of Polymer Brushes journal July 2015
Synthesis of Norbornene Derivative Using Diels-Alder Reaction journal December 2011

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