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Title: Control of polymer architectures by living ring-opening metathesis copolymerization

Abstract

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.

Inventors:
; ; ; ;
Issue Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1840227
Patent Number(s):
11053356
Application Number:
15/914,762
Assignee:
California Institute of Technology (Pasadena, CA)
Patent Classifications (CPCs):
B - PERFORMING OPERATIONS B82 - NANOTECHNOLOGY B82Y - SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES
C - CHEMISTRY C08 - ORGANIC MACROMOLECULAR COMPOUNDS C08F - MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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DOE Contract Number:  
AR0000683; CHE1502616
Resource Type:
Patent
Resource Relation:
Patent File Date: 03/07/2018
Country of Publication:
United States
Language:
English

Citation Formats

Grubbs, Robert H., Lin, Tzu-Pin, Chang, Alice, Chen, Hsiang-Yun, and Bates, Christopher M. Control of polymer architectures by living ring-opening metathesis copolymerization. United States: N. p., 2021. Web.
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Grubbs, Robert H., Lin, Tzu-Pin, Chang, Alice, Chen, Hsiang-Yun, & Bates, Christopher M. Control of polymer architectures by living ring-opening metathesis copolymerization. United States.
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Grubbs, Robert H., Lin, Tzu-Pin, Chang, Alice, Chen, Hsiang-Yun, and Bates, Christopher M. Tue . "Control of polymer architectures by living ring-opening metathesis copolymerization". United States. https://www.osti.gov/servlets/purl/1840227.
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@article{osti_1840227,
title = {Control of polymer architectures by living ring-opening metathesis copolymerization},
author = {Grubbs, Robert H. and Lin, Tzu-Pin and Chang, Alice and Chen, Hsiang-Yun and Bates, Christopher M.},
abstractNote = {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.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Jul 06 00:00:00 EDT 2021},
month = {Tue Jul 06 00:00:00 EDT 2021}
}
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Linear Rheological Response of a Series of Densely Branched Brush Polymers
journal, September 2011

Surface Properties of Bottlebrush Polymer Thin Films
journal, August 2012

Molecular Weight Dependence of Zero-Shear Viscosity in Atactic Polypropylene Bottlebrush Polymers
journal, April 2014

Self-Assembly of Symmetric Brush Diblock Copolymers
journal, February 2013

Block copolymers and conventional lithography
journal, September 2006

Lithium secondary battery
patent, December 2002

Controlling grafting density and side chain length in poly(n-butyl acrylate) by ATRP copolymerization of macromonomers
journal, January 2006

Initiation Efficiency in the Synthesis of Molecular Brushes by Grafting from via Atom Transfer Radical Polymerization
journal, February 2005

Synthesis and Characterization of Single-Ion Graft Copolymer Electrolytes
journal, January 2005

Polymeric photonic band gap materials
patent, August 2002

Enabling nanotechnology with self assembled block copolymer patterns
journal, October 2003

Voltammetric Characterization of the Ferrocene|Ferrocenium and Cobaltocenium|Cobaltocene Redox Couples in RTILs
journal, February 2008

Molecular Brushes with Spontaneous Gradient by Atom Transfer Radical Polymerization
journal, October 2005

Core-Clickable PEG- Branch -Azide Bivalent-Bottle-Brush Polymers by ROMP: Grafting-Through and Clicking-To
journal, January 2011

Driving Mechanisms of Ionic Polymer Actuators Having Electric Double Layer Capacitor Structures
journal, April 2012

Block Copolymer Nanostructures for Technology
journal, October 2010

Synthesis and Melt Self-Assembly of PS–PMMA–PLA Triblock Bottlebrush Copolymers
journal, April 2014

Benchmarking of Homogeneous Electrocatalysts: Overpotential, Turnover Frequency, Limiting Turnover Number
journal, April 2015

Surface Urban Heat Island Across 419 Global Big Cities
journal, December 2011

Synthesis of High Molecular Weight Comb Block Copolymers and Their Assembly into Ordered Morphologies in the Solid State
journal, August 2007

Nanostructured functional materials prepared by atom transfer radical polymerization
journal, June 2009

PEG-grafted chitosan as an injectable thermosensitive hydrogel for sustained protein release
journal, April 2005

Electrocatalytic pathways towards sustainable fuel production from water and CO2
journal, November 2012

Surfactant-induced lyotropic behavior of flexible polymer solutions
journal, May 1993

[Mn(bipyridyl)(CO)3Br]: An Abundant Metal Carbonyl Complex as Efficient Electrocatalyst for CO2 Reduction
journal, September 2011

Theory of Microphase Separation in Block Copolymers
journal, November 1980

Conformation of Cylindrical Brushes in Solution:  Effect of Side Chain Length
journal, November 2006

Polymers of polycyclic olefins having a polyhedral oligosilsesquioxane pendant group and uses thereof
patent-application, September 2005

Improving Brush Polymer Infrared One-Dimensional Photonic Crystals via Linear Polymer Additives
journal, December 2014

On the Self-Assembly of Brush Block Copolymers in Thin Films
journal, October 2013

Synthesis and characterization of a novel ABA triblock copolymer via 4,4′-bis(trifluorovinyloxy)biphenyl and methyl methacrylate
journal, January 2006

Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts †
journal, March 2010

High Toughness, High Conductivity Ion Gels by Sequential Triblock Copolymer Self-Assembly and Chemical Cross-Linking
journal, June 2013

Physical Absorption Of CO 2 in Protic and Aprotic Ionic Liquids: An Interaction Perspective
journal, August 2015

Visualization of MacromoleculesA First Step to Manipulation and Controlled Response
journal, December 2001

Mechanism of the Formation of a Mn-Based CO 2 Reduction Catalyst Revealed by Pulse Radiolysis with Time-Resolved Infrared Detection
journal, April 2014

Copolymerization.
journal, April 1950

Predicting the Flow of Real Polymers
journal, September 2011

Nanoparticles and microparticles of non-linear hydrophilic-hydrophobic multiblock copolymers
patent, December 1999

Polymeric photonic band gap materials
patent, December 2003

Ionically high conductive solid electrolytes composed of graft copolymer-lithium salt hybrids
journal, March 1985

Non-aqueous fluoride salts, solutions, and their uses
patent-application, March 2017

A review on the generation, determination and mitigation of Urban Heat Island
journal, January 2008

Properties of polymer electrolytes composed of poly(ethylene oxide) and ionic liquids according to hard and soft acids and bases theory
journal, March 2011

A three-dimensional photonic crystal operating at infrared wavelengths
journal, July 1998

"Living" titanium(IV) catalyzed coordination polymerizations of isocyanates
journal, June 1991

Application of Bottlebrush Block Copolymers as Photonic Crystals
journal, May 2017

Architecturally Complex Polymers with Controlled Heterogeneity
journal, August 2011

Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties
journal, August 1994

Synthesis and Functionalization of ROMP-Based Gradient Copolymers of 5-Substituted Norbornenes
journal, July 2004

Photonic structures from self assembly of brush block copolymers and polymer blends
patent, September 2016

Super soft elastomers as ionic conductors
journal, August 2004

Synthesis of Li[sup +] Ion Conductive PEO-PSt Block Copolymer Electrolyte with Microphase Separation Structure
journal, January 2005

Unifying Weak- and Strong-Segregation Block Copolymer Theories
journal, January 1996

Advanced applications of ionic liquids in polymer science
journal, May 2009

Static and dynamic properties of two-dimensional polymer melts
journal, January 1990

Electrocatalytic CO 2 reduction with a membrane supported manganese catalyst in aqueous solution
journal, January 2014

Study Concerning the Effects of Chelation on the Structure and Catalytic Activity of Ruthenium Carbene Complexes
journal, January 2002

Impact of urbanization and land-use change on climate
journal, May 2003

Cyclic Block Copolymers for Controlling Feature Sizes in Block Copolymer Lithography
journal, November 2012

Molecular Bottlebrushes: New Opportunities in Nanomaterials Fabrication
journal, September 2012

Living ring-opening metathesis polymerization
journal, January 2007

Patterning with block copolymer thin films
journal, February 2005

Brush copolymers
patent, April 2013

Photonic Polyethylene from Self-Assembled Mesophases of Polydisperse Olefin Block Copolymers
journal, June 2009

Electrical Impedance of Spin-Coatable Ion Gel Films
journal, April 2011

Helical Polymers: Synthesis, Structures, and Functions
journal, November 2009

Periodic nanostructures from self assembled wedge-type block-copolymers
patent, June 2015

Electrocatalytic and homogeneous approaches to conversion of CO 2 to liquid fuels
journal, January 2009

Bottlebrush Block Polymers: Quantitative Theory and Experiments
journal, October 2015

Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis
journal, August 1999

A Local Proton Source Enhances CO 2 Electroreduction to CO by a Molecular Fe Catalyst
journal, October 2012

Theory of microphase separation in graft and star copolymers
journal, October 1986

Conformational Analysis of Olefin−Carbene Ruthenium Metathesis Catalysts
journal, April 2009

Plasmonics for improved photovoltaic devices
journal, February 2010

Noncovalent Immobilization of Electrocatalysts on Carbon Electrodes for Fuel Production
journal, November 2013

Splitting CO2 into CO and O2 by a single catalyst
journal, June 2012

Self-Assembled Photonic Structures
journal, September 2010

Dynamic Cylindrical Assembly of Triblock Copolymers by a Hierarchical Process of Covalent and Supramolecular Interactions
journal, February 2011

Computer Simulations of Bottle Brushes: From Melts to Soft Networks
journal, July 2015

Molecular Rheology of Comb Polymer Melts. 1. Linear Viscoelastic Response
journal, September 2001

Helical polymer brushes with a preferred-handed helix-sense triggered by a terminal optically active group in the pendant
journal, January 2012

Thermodynamic Properties of Block Copolymer Electrolytes Containing Imidazolium and Lithium Salts
journal, October 2010

Investigation of the Assembly of Comb Block Copolymers in the Solid State
journal, October 2008

Mechanisms for CO Production from CO 2 Using Reduced Rhenium Tricarbonyl Catalysts
journal, March 2012

Aluminum nanowire polarizing grids: Fabrication and analysis
journal, May 2006

ABA-triblock copolymer ion gels for CO2 separation applications
journal, December 2012

Ionic liquids: applications in catalysis
journal, May 2002

Intramolecular Hydroamination of Aminoalkynes with Silver−Phenanthroline Catalysts
journal, September 2008

Rapid self-assembly of block copolymers to photonic crystals
patent-application, December 2013

Reactivity of Macromonomers in free Radical Polymerization
journal, August 1990

Self-assembly of block copolymers
journal, January 2012

Linear method for determining monomer reactivity ratios in copolymerization
journal, April 1950

Block Copolymers—Designer Soft Materials
journal, February 1999

Ionic Liquid Co-catalyzed Artificial Photosynthesis of CO
journal, January 2013

Smart polymer brushes and their emerging applications
journal, January 2012

Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes
journal, December 1994

Review of gel-type polymer electrolytes for lithium-ion batteries
journal, February 1999

Triblock brush block copolymers
patent-application, October 2016

Coarse-grained simulations of ABA amphiphilic triblock copolymer solutions in thin films
journal, January 2007

Structural investigations into the deactivation pathway of the CO2 reduction electrocatalyst Re(bpy)(CO)3Cl
journal, January 2012

Crystallization and thermal properties of PLLA comb polymer
journal, March 2008

Electrochemical cell with a grahite intercalation compound cathode
patent, October 1977

Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns
journal, July 2009

Inorganic block co-polymers and other similar materials as ceramic precursors for nanoscale ordered high-temperature ceramics
patent-application, May 2007

Reactivity of a fac-ReCl(α-diimine)(CO) 3 complex with an NAD + model ligand toward CO 2 reduction
journal, January 2014

Control of gradient copolymer composition in ATRP using semibatch feeding policy
journal, January 2006

Small-Angle Neutron Scattering Analysis of Bottlebrush Polymers Prepared via Grafting-Through Polymerization
journal, August 2013

Removal of Palladium from Organic Reaction Mixtures by Trimercaptotriazine
journal, July 1997

Ionic liquids as electrolytes
journal, August 2006

Characteristics of new-type solid polymer electrolyte controlling nano-structure
journal, August 2005

Polymer Compositions Based on PXE
patent-application, January 2016

Melts of semiflexible diblock copolymer
journal, May 1996

Structure, function, self-assembly, and applications of bottlebrush copolymers
journal, January 2015

Stimuli-responsive molecular brushes
journal, January 2010

Transfer-matrix formalism for the calculation of optical response in multilayer systems: from coherent to incoherent interference
journal, January 2010

Structural and Mechanistic Basis of the Fast Metathesis Initiation by a Six-Coordinated Ruthenium Catalyst
journal, June 2013

Hierarchical self-assembly of metal nanostructures on diblock copolymer scaffolds
journal, December 2001

Periodic Nanostructures From Self Assembled Wedge-Type Block-Copolymers
patent-application, November 2013

Self-aligned self assembly of multi-nanowire silicon field effect transistors
journal, October 2005

Efficient Synthesis of Narrowly Dispersed Brush Copolymers and Study of Their Assemblies: The Importance of Side Chain Arrangement
journal, December 2009

Facile Analysis of EC Cyclic Voltammograms
journal, March 2004

Synthesis of Polymer Dielectric Layers for Organic Thin Film Transistors via Surface-Initiated Ring-Opening Metathesis Polymerization
journal, April 2004

Nonlinear rheology of model comb polymers
journal, September 2009

Ion Gel Gated Polymer Thin-Film Transistors
journal, April 2007

ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties
journal, July 2015

Optically Transparent and High Molecular Weight Polyolefin Block Copolymers toward Self-Assembled Photonic Band Gap Materials
journal, March 2006

Synergistic Increase in Ionic Conductivity and Modulus of Triblock Copolymer Ion Gels
journal, July 2015

Efficient Synthesis of Narrowly Dispersed Brush Polymers via Living Ring-Opening Metathesis Polymerization of Macromonomers
journal, June 2009

Towards a methanol economy based on homogeneous catalysis: methanol to H 2 and CO 2 to methanol
journal, January 2015

Synthesis and photophysical and electrochemical properties of new halotricarbonyl(polypyridine)rhenium(I) complexes
journal, November 1988

Fabricating complex three-dimensional nanostructures with high-resolution conformable phase masks
journal, August 2004

Phase Behavior and Morphological Characteristics of Compositionally Symmetric Diblock Copolymer Blends
journal, January 1996

Macromolecular stereochemistry: the out-of-proportion influence of optically active comonomers on the conformational characteristics of polyisocyanates. The sergeants and soldiers experiment
journal, August 1989

Brush copolymers
patent, June 2013

Electrocatalytic CO 2 Reduction with a Homogeneous Catalyst in Ionic Liquid: High Catalytic Activity at Low Overpotential
journal, May 2014

Structural Transition in an Ionic Liquid Controls CO 2 Electrochemical Reduction
journal, July 2015

Block copolymer electrolytes for rechargeable lithium batteries
journal, November 2013

Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes
journal, January 2013

Electrocatalytic reduction of carbon dioxide on a cobalt tetrakis(4-aminophenyl)porphyrin modified electrode in BMImBF 4
journal, January 2014

New Directions for the Photocatalytic Reduction of CO 2 : Supramolecular, scCO 2 or Biphasic Ionic Liquid−scCO 2 Systems
journal, September 2010

Nanostructure fabrication using block copolymers
journal, September 2003

Electroactive Block Copolymer Brushes on Multiwalled Carbon Nanotubes
journal, August 2009

Effect of Side Chain Rigidity on the Elasticity of Comb Copolymer Cylindrical Brushes:  A Monte Carlo Simulation Study
journal, June 1999

Templated Self-Assembly of Block Copolymers: Top-Down Helps Bottom-Up
journal, October 2006

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