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Title: 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 Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Organization:
USDOE; National Science Foundation (NSF)
DOE Contract Number:
AR0000683; CHE1502616
Assignee:
California Institute of Technology (Pasadena, CA)
Patent Number(s):
11,053,356
Application Number:
15/914,762
OSTI ID:
1840227
Resource Relation:
Patent File Date: 03/07/2018
Country of Publication:
United States
Language:
English

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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
Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO 2 with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center journal August 2015
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
Polystyrene- block -poly(ethylene oxide) Bottlebrush Block Copolymer Morphology Transitions: Influence of Side Chain Length and Volume Fraction journal February 2017
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
A Phase Diagram for the Binary Blends of Nearly Symmetric Diblock Copolymers. 1. Parameter Space of Molecular Weight Ratio and Blend Composition journal August 2001
"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
Effect of Dense Grafting on the Backbone Conformation of Bottlebrush Polymers:  Determination of the Persistence Length in Solution journal November 2002
Electrochemical behaviors and spectral studies of ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) based sol–gel electrode journal May 2007
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
⅔ -Power Law for Copolymer Lamellar Thickness Implies a ⅓ -Power Law for Spinodal Decomposition journal August 1988
Conductivities of solid polymer electrolyte complexes of alkali salts with polymers of methoxypolyethyleneglycol methacrylates journal November 1984
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
Formation of Alternating trans - A - alt - B Copolymers through Ring-Opening Metathesis Polymerization Initiated by Molybdenum Imido Alkylidene Complexes journal July 2015
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
Involvement of a Binuclear Species with the Re−C(O)O−Re Moiety in CO 2 Reduction Catalyzed by Tricarbonyl Rhenium(I) Complexes with Diimine Ligands:  Strikingly Slow Formation of the Re−Re and Re−C(O)O−Re Species from Re(dmb)(CO) 3 S (dmb = 4,4‘-Dimethyl-2,2‘-bipyridine, S = Solvent) journal October 2003
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
Effect of side chain length and crosslinking on the ac conductivity of oligo (ethyleneoxide) comb-branch polymer-salt mixtures journal October 1990
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
Particles comprising amphiphilic copolymers, having a crosslinked shell domain and an interior core domain, useful for pharmaceutical and other applications patent May 2002
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
The effect of different lithium salts on conductivity of comb-like polymer electrolyte with chelating functional group journal February 2003
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
Polymer brushes for immobilizing molecules to a surface or substrate, where the polymers have water-soluble or water-dispersible segments and probes bonded thereto patent February 2004
Bi- and Trinuclear Ruthenium Alkylidene Triggered Cyclopolymerization of 1,6-Heptadiynes:  Access to A n −X−A n Block and (A n ) 3 X Tristar Copolymers journal May 2006
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
Nanocomposite hydrogels based on liquid crystalline brush-like block copolymer–Au nanorods and their application in H2O2 detection journal January 2015
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
Electrochemistry of tris(2,2′-bipyridyl) cobalt(II) in ionic liquids and aprotic molecular solvents on glassy carbon and platinum electrodes journal October 2015
Ultrahigh Molecular Weight Linear Block Copolymers: Rapid Access by Reversible-Deactivation Radical Polymerization and Self-Assembly into Large Domain Nanostructures journal May 2016
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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