Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition

Levi, Adam E.; Lequieu, Joshua; Horne, Jacob D.; Bates, Morgan W.; Ren, Jing M.; Delaney, Kris T.; Fredrickson, Glenn H.; Bates, Christopher M.

doi:10.1021/acs.macromol.8b02321

Title: Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition

Journal Article · 12 February 2019 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.8b02321 · OSTI ID:1594102

Levi, Adam E. ^[1]; Lequieu, Joshua ^[2]; Horne, Jacob D. ^[2];

^[2]; Ren, Jing M. ^[2];

^[2];

^[2]

Univ. of California, Santa Barbara, CA (United States); University of California, Santa Barbara
Univ. of California, Santa Barbara, CA (United States)

The grafting-through copolymerization of two distinct macromonomers via ring-opening metathesis polymerization is normally used to form statistical or diblock bottlebrush polymers with large total backbone degrees of polymerization (N_BB) relative to that of the side-chains (N_SC). Here, we demonstrate that Grubbs-type chemistry in the opposite limit, namely N_BB << N_SC, produces well-defined materials with excellent control over ensemble-averaged properties, including molar mass, dispersity, composition, and number of branch points. The dependence of self-assembly on these molecular design parameters was systematically probed using small angle X-ray scattering and self-consistent field theoretic simulations. Moreover, our analysis supports the notion that two-component bottlebrush copolymers with small N_BB behave like miktoarm star polymers. The star-to-bottlebrush transition is quantifiable for both statistical and diblock sequences by unique signatures in the experimental scaling of domain spacing and simulated distribution of backbone/side-chain density within lamellar unit cells. These findings represent a conceptual framework that simplifies the synthesis of miktoarm star polymers when dispersity in the number of arms and composition can be tolerated. The analytical approach introduced to distinguish chain conformations in complex macromolecules also complements previous methods, for example form factor scattering and rheology.

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Research Organization:: Univ. of California, Santa Barbara, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0019001

OSTI ID:: 1594102

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 4 Vol. 52; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

A Practical and Highly Active Ruthenium-Based Catalyst that Effects the Cross Metathesis of Acrylonitrile Love, Jennifer A.; Morgan, John P.; Trnka, Tina M. Angewandte Chemie International Edition, Vol. 41, Issue 21 https://doi.org/10.1002/1521-3773(20021104)41:21<4035::AID-ANIE4035>3.0.CO;2-I	journal	November 2002
Bottlebrush Elastomers: A New Platform for Freestanding Electroactuation Vatankhah-Varnoosfaderani, Mohammad; Daniel, William F. M.; Zhushma, Alexandr P. Advanced Materials, Vol. 29, Issue 2 https://doi.org/10.1002/adma.201604209	journal	November 2016
Janus Graft Block Copolymers: Design of a Polymer Architecture for Independently Tuned Nanostructures and Polymer Properties Guo, Zi-Hao; Le, An N.; Feng, Xunda Angewandte Chemie International Edition, Vol. 57, Issue 28 https://doi.org/10.1002/anie.201802844	journal	May 2018
Brush-First Synthesis of Core-Photodegradable Miktoarm Star Polymers via ROMP: Towards Photoresponsive Self-Assemblies Burts, Alan O.; Gao, Angela X.; Johnson, Jeremiah A. Macromolecular Rapid Communications, Vol. 35, Issue 2 https://doi.org/10.1002/marc.201300618	journal	November 2013
Syntheses of triblock bottlebrush polymers through sequential ROMPs: Expanding the functionalities of molecular brushes: RAPID COMMUNICATION Su, Lu; Heo, Gyu Seong; Lin, Yen-Nan Journal of Polymer Science Part A: Polymer Chemistry, Vol. 55, Issue 18 https://doi.org/10.1002/pola.28647	journal	May 2017
Brush polymer ion gels Bates, Christopher M.; Chang, Alice B.; Schulze, Morgan W. Journal of Polymer Science Part B: Polymer Physics, Vol. 54, Issue 2 https://doi.org/10.1002/polb.23927	journal	October 2015
Block copolymer micelles for drug delivery: Design, characterization and biological significance Kataoka, Kazunori; Harada, Atsushi; Nagasaki, Yukio Advanced Drug Delivery Reviews, Vol. 64 https://doi.org/10.1016/j.addr.2012.09.013	journal	December 2012
Strong, Resilient, and Sustainable Aliphatic Polyester Thermoplastic Elastomers Watts, Annabelle; Kurokawa, Naruki; Hillmyer, Marc A. Biomacromolecules, Vol. 18, Issue 6 https://doi.org/10.1021/acs.biomac.7b00283	journal	May 2017
50th Anniversary Perspective : Block Polymers—Pure Potential Bates, Christopher M.; Bates, Frank S. Macromolecules, Vol. 50, Issue 1 https://doi.org/10.1021/acs.macromol.6b02355	journal	December 2016
Brush-First and ROMP-Out with Functional (Macro)monomers: Method Development, Structural Investigations, and Applications of an Expanded Brush-Arm Star Polymer Platform Golder, Matthew R.; Nguyen, Hung V. -T.; Oldenhuis, Nathan J. Macromolecules, Vol. 51, Issue 23 https://doi.org/10.1021/acs.macromol.8b01966	journal	November 2018
Templated Self-Assembly of a PS- Branch -PDMS Bottlebrush Copolymer Cheng, Li-Chen; Gadelrab, Karim R.; Kawamoto, Ken Nano Letters, Vol. 18, Issue 7 https://doi.org/10.1021/acs.nanolett.8b01389	journal	June 2018
Nitroxide-Based Macromolecular Contrast Agents with Unprecedented Transverse Relaxivity and Stability for Magnetic Resonance Imaging of Tumors Nguyen, Hung V. -T.; Chen, Qixian; Paletta, Joseph T. ACS Central Science, Vol. 3, Issue 7 https://doi.org/10.1021/acscentsci.7b00253	journal	July 2017
Mikto-Brush-Arm Star Polymers via Cross-Linking of Dissimilar Bottlebrushes: Synthesis and Solution Morphologies Shibuya, Yoshiki; Nguyen, Hung V. -T.; Johnson, Jeremiah A. ACS Macro Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acsmacrolett.7b00529	journal	August 2017
Bottlebrush Block Polymers: Quantitative Theory and Experiments Dalsin, Samuel J.; Rions-Maehren, Thomas G.; Beam, Marissa D. ACS Nano, Vol. 9, Issue 12 https://doi.org/10.1021/acsnano.5b05473	journal	October 2015
Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush Lin, Tzu-Pin; Chang, Alice B.; Luo, Shao-Xiong ACS Nano, Vol. 11, Issue 11 https://doi.org/10.1021/acsnano.7b06664	journal	September 2017
Triply Loaded Nitroxide Brush-Arm Star Polymers Enable Metal-Free Millimetric Tumor Detection by Magnetic Resonance Imaging Nguyen, Hung V. -T.; Detappe, Alexandre; Gallagher, Nolan M. ACS Nano, Vol. 12, Issue 11 https://doi.org/10.1021/acsnano.8b06160	journal	November 2018
Block Copolymer Based Nanostructures: Materials, Processes, and Applications to Electronics Kim, Ho-Cheol; Park, Sang-Min; Hinsberg, William D. Chemical Reviews, Vol. 110, Issue 1 https://doi.org/10.1021/cr900159v	journal	January 2010
Synthesis of High Molecular Weight Comb Block Copolymers and Their Assembly into Ordered Morphologies in the Solid State Runge, M. Brett; Bowden, Ned B. Journal of the American Chemical Society, Vol. 129, Issue 34 https://doi.org/10.1021/ja072929q	journal	August 2007
Dynamic Cylindrical Assembly of Triblock Copolymers by a Hierarchical Process of Covalent and Supramolecular Interactions Li, Zhou; Ma, Jun; Lee, Nam S. Journal of the American Chemical Society, Vol. 133, Issue 5 https://doi.org/10.1021/ja109191z	journal	February 2011
Unexpected Consequences of Block Polydispersity on the Self-Assembly of ABA Triblock Copolymers Widin, Joan M.; Schmitt, Adam K.; Schmitt, Andrew L. Journal of the American Chemical Society, Vol. 134, Issue 8 https://doi.org/10.1021/ja210548e	journal	February 2012
“Brush-First” Method for the Parallel Synthesis of Photocleavable, Nitroxide-Labeled Poly(ethylene glycol) Star Polymers Liu, Jenny; Burts, Alan O.; Li, Yongjun Journal of the American Chemical Society, Vol. 134, Issue 39 https://doi.org/10.1021/ja3067176	journal	September 2012
Nanoscopic Cylindrical Dual Concentric and Lengthwise Block Brush Terpolymers as Covalent Preassembled High-Resolution and High-Sensitivity Negative-Tone Photoresist Materials Sun, Guorong; Cho, Sangho; Clark, Corrie Journal of the American Chemical Society, Vol. 135, Issue 11 https://doi.org/10.1021/ja3126382	journal	March 2013
A Convergent Synthetic Platform for Single-Nanoparticle Combination Cancer Therapy: Ratiometric Loading and Controlled Release of Cisplatin, Doxorubicin, and Camptothecin Liao, Longyan; Liu, Jenny; Dreaden, Erik C. Journal of the American Chemical Society, Vol. 136, Issue 16 https://doi.org/10.1021/ja502011g	journal	April 2014
Aqueous Self-Assembly of Giant Bottlebrush Block Copolymer Surfactants as Shape-Tunable Building Blocks Fenyves, Ryan; Schmutz, Marc; Horner, Ian J. Journal of the American Chemical Society, Vol. 136, Issue 21 https://doi.org/10.1021/ja503283r	journal	May 2014
Efficient Synthesis of Narrowly Dispersed Brush Copolymers and Study of Their Assemblies: The Importance of Side Chain Arrangement Xia, Yan; Olsen, Bradley D.; Kornfield, Julia A. Journal of the American Chemical Society, Vol. 131, Issue 51, p. 18525-18532 https://doi.org/10.1021/ja908379q	journal	December 2009
Providing Oligonucleotides with Steric Selectivity by Brush-Polymer-Assisted Compaction Lu, Xueguang; Tran, Thanh-Huyen; Jia, Fei Journal of the American Chemical Society, Vol. 137, Issue 39 https://doi.org/10.1021/jacs.5b08069	journal	September 2015
Using an RNAi Signature Assay To Guide the Design of Three-Drug-Conjugated Nanoparticles with Validated Mechanisms, In Vivo Efficacy, and Low Toxicity Barnes, Jonathan C.; Bruno, Peter M.; Nguyen, Hung V. -T. Journal of the American Chemical Society, Vol. 138, Issue 38 https://doi.org/10.1021/jacs.6b06321	journal	September 2016
Graft-through Synthesis and Assembly of Janus Bottlebrush Polymers from A- Branch -B Diblock Macromonomers Kawamoto, Ken; Zhong, Mingjiang; Gadelrab, Karim R. Journal of the American Chemical Society, Vol. 138, Issue 36 https://doi.org/10.1021/jacs.6b07670	journal	September 2016
Control of Grafting Density and Distribution in Graft Polymers by Living Ring-Opening Metathesis Copolymerization Lin, Tzu-Pin; Chang, Alice B.; Chen, Hsiang-Yun Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.7b00791	journal	March 2017
Synthesis of a model 3-miktoarm star terpolymer Iatrou, Hermis; Hadjichristidis, Nikos Macromolecules, Vol. 25, Issue 18 https://doi.org/10.1021/ma00044a028	journal	August 1992
Chain Architecture and Asymmetry in Copolymer Microphases Milner, Scott T. Macromolecules, Vol. 27, Issue 8 https://doi.org/10.1021/ma00086a057	journal	April 1994
Melt Chain Dimensions of Polylactide Anderson, Kelly S.; Hillmyer, Marc A. Macromolecules, Vol. 37, Issue 5 https://doi.org/10.1021/ma0357523	journal	March 2004
Interfaces in Diblocks: A Study of Miktoarm Star Copolymers Grason, Gregory M.; Kamien, Randall D. Macromolecules, Vol. 37, Issue 19 https://doi.org/10.1021/ma049255d	journal	September 2004
Synthesis of Ultralarge Molecular Weight Bottlebrush Polymers Using Grubbs' Catalysts Jha, Sheuli; Dutta, Samrat; Bowden, Ned B. Macromolecules, Vol. 37, Issue 12 https://doi.org/10.1021/ma049647k	journal	May 2004
Drug-Loaded, Bivalent-Bottle-Brush Polymers by Graft-through ROMP Johnson, Jeremiah A.; Lu, Ying Y.; Burts, Alan O. Macromolecules, Vol. 43, Issue 24 https://doi.org/10.1021/ma1021506	journal	December 2010
Small-Angle Neutron Scattering Analysis of Bottlebrush Polymers Prepared via Grafting-Through Polymerization Pesek, Stacy L.; Li, Xianyu; Hammouda, Boualem Macromolecules, Vol. 46, Issue 17 https://doi.org/10.1021/ma401246b	journal	August 2013
Toward Strong Thermoplastic Elastomers with Asymmetric Miktoarm Block Copolymer Architectures Shi, Weichao; Lynd, Nathaniel A.; Montarnal, Damien Macromolecules, Vol. 47, Issue 6 https://doi.org/10.1021/ma402566g	journal	March 2014
Efficient Synthesis of Narrowly Dispersed Brush Polymers via Living Ring-Opening Metathesis Polymerization of Macromonomers Xia, Yan; Kornfield, Julia A.; Grubbs, Robert H. Macromolecules, Vol. 42, Issue 11, p. 3761-3766 https://doi.org/10.1021/ma900280c	journal	June 2009
Molecular Weight Dependence of Zero-Shear Viscosity in Atactic Polypropylene Bottlebrush Polymers Dalsin, Samuel J.; Hillmyer, Marc A.; Bates, Frank S. ACS Macro Letters, Vol. 3, Issue 5 https://doi.org/10.1021/mz500082h	journal	April 2014
σ Phase Formed in Conformationally Asymmetric AB-Type Block Copolymers Xie, Nan; Li, Weihua; Qiu, Feng ACS Macro Letters, Vol. 3, Issue 9 https://doi.org/10.1021/mz500445v	journal	August 2014
Self-Assembly of Symmetric Brush Diblock Copolymers Gu, Weiyin; Huh, June; Hong, Sung Woo ACS Nano, Vol. 7, Issue 3 https://doi.org/10.1021/nn305867d	journal	February 2013
Redox-responsive branched-bottlebrush polymers for in vivo MRI and fluorescence imaging Sowers, Molly A.; McCombs, Jessica R.; Wang, Ying Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6460	journal	November 2014
Block copolymers in tomorrow's plastics Ruzette, Anne-Valérie; Leibler, Ludwik Nature Materials, Vol. 4, Issue 1 https://doi.org/10.1038/nmat1295	journal	January 2005
Reduction of liver fibrosis by rationally designed macromolecular telmisartan prodrugs Golder, Matthew R.; Liu, Jenny; Andersen, Jannik N. Nature Biomedical Engineering, Vol. 2, Issue 11 https://doi.org/10.1038/s41551-018-0279-x	journal	August 2018
Morphology of miktoarm star block copolymers of styrene and isoprene Tselikas, Y.; Iatrou, H.; Hadjichristidis, N. The Journal of Chemical Physics, Vol. 105, Issue 6 https://doi.org/10.1063/1.472113	journal	August 1996
Block Copolymers—Designer Soft Materials Bates, Frank S.; Fredrickson, Glenn H. Physics Today, Vol. 52, Issue 2 https://doi.org/10.1063/1.882522	journal	February 1999
Rapid self-assembly of brush block copolymers to photonic crystals Sveinbjornsson, B. R.; Weitekamp, R. A.; Miyake, G. M. Proceedings of the National Academy of Sciences, Vol. 109, Issue 36, p. 14332-14336 https://doi.org/10.1073/pnas.1213055109	journal	August 2012
Multiblock Polymers: Panacea or Pandora's Box? Bates, F. S.; Hillmyer, M. A.; Lodge, T. P. Science, Vol. 336, Issue 6080 https://doi.org/10.1126/science.1215368	journal	April 2012
Sequence-Controlled Polymers Lutz, J. -F.; Ouchi, M.; Liu, D. R. Science, Vol. 341, Issue 6146 https://doi.org/10.1126/science.1238149	journal	August 2013
Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration Vatankhah-Varnosfaderani, Mohammad; Keith, Andrew N.; Cong, Yidan Science, Vol. 359, Issue 6383 https://doi.org/10.1126/science.aar5308	journal	March 2018

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Theoretical prediction of an isotropic to nematic phase transition in bottlebrush homopolymer melts Panagiotou, Eleni; Delaney, Kris T.; Fredrickson, Glenn H. The Journal of Chemical Physics, Vol. 151, Issue 9 https://doi.org/10.1063/1.5114698	journal	September 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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grafting-through polymerization
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miktoarm star
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star transition

Title: Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition

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