Monitoring morphology evolution within block copolymer microparticles during dispersion polymerisation in supercritical carbon dioxide: a high pressure SAXS study

Alauhdin, Mohammad; Bennett, Thomas M.; He, Guping; Bassett, Simon P.; Portale, Giuseppe; Bras, Wim; Hermida-Merino, Daniel; Howdle, Steven M.

doi:10.1039/c8py01578c

Title: Monitoring morphology evolution within block copolymer microparticles during dispersion polymerisation in supercritical carbon dioxide: a high pressure SAXS study

Journal Article · Tue Jan 01 00:00:00 EST 2019 · Polymer Chemistry

DOI:https://doi.org/10.1039/c8py01578c· OSTI ID:1494887

Alauhdin, Mohammad ^[1];

^[1]; He, Guping ^[1]; Bassett, Simon P. ^[1];

^[2];

^[3]; Hermida-Merino, Daniel ^[4];

^[1]

Univ. of Nottingham (United Kingdom). School of Chemistry
Univ. of Groningen (The Netherlands). Zernike Inst. for Advanced Materials
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Netherlands Organisation for Scientific Research (N.W.O), Grenoble (France)

Reversible addition-fragmentation chain transfer (RAFT) dispersion polymerisation in supercritical carbon dioxide is an effective process for creating block copolymer microparticles with internal nanostructures. Here we report an alternative synthesis route involving completely independent steps by exploiting the livingness of RAFT-terminated PMMA microparticles and their unique ability to be redispersed in scCO₂. This not only enables a series of block copolymers to be created from a single RAFT dispersion synthesised PMMA homopolymer batch, thus improving reproducibility, but also adds flexibility by allowing the time and concentration requirements for each stage to be decoupled. The internal morphology development and evolution for a series of poly(methyl methacrylate-block-styrene) (PMMA-b-PS) block copolymer microparticles synthesised via this route was monitored via in situ small-angle X-ray scattering (SAXS) using an autoclave with diamond windows. Together with offline kinetics experiments and post-mortem transmission electron microscopy imaging, this study provides remarkably detailed insights into block copolymer self-organisation phenomena in scCO₂. Specifically, the time period over which this block copolymer undergoes phase separation before progressing from an arrangement of spheres to lamellae via the hexagonal cylinder phase is elucidated, and the data are used to plot a detailed empirical phase diagram for this block copolymer system in scCO₂.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1494887

Journal Information:: Polymer Chemistry, Vol. 10, Issue 7; ISSN 1759-9954

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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References (65)

How does dense phase CO ₂ influence the phase behaviour of block copolymers synthesised by dispersion polymerisation? Jennings, J.; Bassett, S. P.; Hermida-Merino, D. Polymer Chemistry, Vol. 7, Issue 4 https://doi.org/10.1039/C5PY01823D	journal	January 2016
Polymer–supercritical fluid interactions Kikic, I. The Journal of Supercritical Fluids, Vol. 47, Issue 3 https://doi.org/10.1016/j.supflu.2008.10.016	journal	January 2009
Synchrotron SAXS study on the micro-phase separation kinetics of segmented block copolymer Lee, Han Sup; Yoo, So Ra; Seo, Seung Won Fibers and Polymers, Vol. 2, Issue 2 https://doi.org/10.1007/BF02875266	journal	June 2001
Kinetics of Hexagonal−Body-Centered Cubic Transition in a Triblock Copolymer in a Selective Solvent: Time-Resolved Small-Angle X-ray Scattering Measurements and Model Calculations Li, Minghai; Liu, Yongsheng; Nie, Huifen Macromolecules, Vol. 40, Issue 26 https://doi.org/10.1021/ma0716276	journal	December 2007
Polymerization-Induced Self-Assembly: From Soluble Macromolecules to Block Copolymer Nano-Objects in One Step Charleux, Bernadette; Delaittre, Guillaume; Rieger, Jutta Macromolecules, Vol. 45, Issue 17 https://doi.org/10.1021/ma300713f	journal	June 2012
Advantages of Block Copolymer Synthesis by RAFT-Controlled Dispersion Polymerization in Supercritical Carbon Dioxide Jennings, James; Beija, Mariana; Kennon, Jeremy T. Macromolecules, Vol. 46, Issue 17 https://doi.org/10.1021/ma401051e	journal	August 2013
Inorganic Gyroid with Exceptionally Low Refractive Index from Block Copolymer Templating Hsueh, Han-Yu; Chen, Hung-Ying; She, Ming-Shiuan Nano Letters, Vol. 10, Issue 12 https://doi.org/10.1021/nl103104w	journal	December 2010
Solvent-Driven Evolution of Block Copolymer Morphology under 3D Confinement Li, Le; Matsunaga, Kazuyuki; Zhu, Jintao Macromolecules, Vol. 43, Issue 18 https://doi.org/10.1021/ma101529b	journal	September 2010
Sorption and swelling of block copolymers in the presence of supercritical fluid carbon dioxide Zhang, Yi; Gangwani, Kishore K.; Lemert, Richard M. The Journal of Supercritical Fluids, Vol. 11, Issue 1-2 https://doi.org/10.1016/S0896-8446(97)00031-4	journal	October 1997
Polymerization-induced self-assembly of block copolymer nanoparticles via RAFT non-aqueous dispersion polymerization Derry, Matthew J.; Fielding, Lee A.; Armes, Steven P. Progress in Polymer Science, Vol. 52 https://doi.org/10.1016/j.progpolymsci.2015.10.002	journal	January 2016
Small-Angle X-ray Scattering of Polymers Chu, Benjamin; Hsiao, Benjamin S. Chemical Reviews, Vol. 101, Issue 6 https://doi.org/10.1021/cr9900376	journal	June 2001
Morphological Phase Behavior of Poly(RTIL)-Containing Diblock Copolymer Melts Scalfani, Vincent F.; Wiesenauer, Erin F.; Ekblad, John R. Macromolecules, Vol. 45, Issue 10 https://doi.org/10.1021/ma300328u	journal	April 2012
Theory of Microphase Separation in Block Copolymers Leibler, Ludwik Macromolecules, Vol. 13, Issue 6 https://doi.org/10.1021/ma60078a047	journal	November 1980
Functional Polymers from Novel Carboxyl-Terminated Trithiocarbonates as Highly Efficient RAFT Agents Lai, John T.; Filla, Debby; Shea, Ronald Macromolecules, Vol. 35, Issue 18 https://doi.org/10.1021/ma020362m	journal	August 2002
Conductivity Scaling Relationships for Nanostructured Block Copolymer/Ionic Liquid Membranes Hoarfrost, Megan L.; Segalman, Rachel A. ACS Macro Letters, Vol. 1, Issue 8 https://doi.org/10.1021/mz300241g	journal	July 2012
The Full Phase Behavior for Block Copolymers in Solvents of Varying Selectivity Lodge, Timothy P.; Pudil, Bryant; Hanley, Kenneth J. Macromolecules, Vol. 35, Issue 12 https://doi.org/10.1021/ma0200975	journal	June 2002
Hierarchically Structured Materials from Block Polymer Confinement within Bicontinuous Microemulsion-Derived Nanoporous Polyethylene Jones, Brad H.; Lodge, Timothy P. ACS Nano, Vol. 5, Issue 11 https://doi.org/10.1021/nn203096x	journal	October 2011
Asymmetric superstructure formed in a block copolymer via phase separation Peinemann, Klaus-Viktor; Abetz, Volker; Simon, Peter F. W. Nature Materials, Vol. 6, Issue 12 https://doi.org/10.1038/nmat2038	journal	November 2007
Input of supercritical carbon dioxide to polymer synthesis: An overview Boyère, Cédric; Jérôme, Christine; Debuigne, Antoine European Polymer Journal, Vol. 61 https://doi.org/10.1016/j.eurpolymj.2014.07.019	journal	December 2014
One-Pot Synthesis of Block Copolymers in Supercritical Carbon Dioxide: A Simple Versatile Route to Nanostructured Microparticles Jennings, James; Beija, Mariana; Richez, Alexandre P. Journal of the American Chemical Society, Vol. 134, Issue 10 https://doi.org/10.1021/ja210577h	journal	February 2012
Temperature dependence of the interaction parameter of polystyrene and poly(methyl methacrylate) Russell, Thomas P.; Hjelm, Rex P.; Seeger, Phil A. Macromolecules, Vol. 23, Issue 3 https://doi.org/10.1021/ma00205a033	journal	May 1990
Hierarchical Porous Polymer Scaffolds from Block Copolymers Sai, H.; Tan, K. W.; Hur, K. Science, Vol. 341, Issue 6145 https://doi.org/10.1126/science.1238159	journal	August 2013
Patterning with block copolymer thin films Segalman, Rachel A. Materials Science and Engineering: R: Reports, Vol. 48, Issue 6, p. 191-226 https://doi.org/10.1016/j.mser.2004.12.003	journal	February 2005
Spontaneous formation of polymer nanoparticles with inner micro-phase separation structures Higuchi, Takeshi; Tajima, Atsunori; Yabu, Hiroshi Soft Matter, Vol. 4, Issue 6 https://doi.org/10.1039/b800904j	journal	January 2008
A Synchrotron SAXS Study of Structure Development Kinetics during the Reactive Processing of Flexible Polyurethane Foam Elwell, Michael J.; Mortimer, Stephen; Ryan, Anthony J. Macromolecules, Vol. 27, Issue 19 https://doi.org/10.1021/ma00097a024	journal	September 1994
Nanostructures Inside Colloidal Particles of Block Copolymer/Homopolymer Blends Jeon, Seog-Jin; Yi, Gi-Ra; Koo, Chong Min Macromolecules, Vol. 40, Issue 23 https://doi.org/10.1021/ma0712302	journal	November 2007
Experimental research on swelling and glass transition behavior of poly(methyl methacrylate) in supercritical carbon dioxide Li, Ruosong; Zhang, Zhonghui; Fang, Tao The Journal of Supercritical Fluids, Vol. 110 https://doi.org/10.1016/j.supflu.2015.12.017	journal	April 2016
Phase Behavior of Polystyrene- b -poly(methyl methacrylate) Diblock Copolymer Ahn, Hyungju; Ryu, Du Yeol; Kim, Youngmin Macromolecules, Vol. 42, Issue 20 https://doi.org/10.1021/ma901313a	journal	October 2009
Can ionic liquid additives be used to extend the scope of poly(styrene)-block-poly(methyl methacrylate) for directed self-assembly? Bennett, Thomas M.; Pei, Kevin; Cheng, Han-Hao Journal of Micro/Nanolithography, MEMS, and MOEMS, Vol. 13, Issue 3 https://doi.org/10.1117/1.JMM.13.3.031304	journal	July 2014
Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems Jennings, J.; He, G.; Howdle, S. M. Chemical Society Reviews, Vol. 45, Issue 18 https://doi.org/10.1039/C6CS00253F	journal	January 2016
Block copolymers as photonic bandgap materials Fink, Y.; Urbas, A. M.; Bawendi, M. G. Journal of Lightwave Technology, Vol. 17, Issue 11, p. 1963-1969 https://doi.org/10.1109/50.802981	journal	November 1999
Unifying Weak- and Strong-Segregation Block Copolymer Theories Matsen, M. W.; Bates, F. S. Macromolecules, Vol. 29, Issue 4 https://doi.org/10.1021/ma951138i	journal	January 1996
Simultaneous measurement of the solubility of nitrogen and carbon dioxide in polystyrene and of the associated polymer swelling: Solubility of Nitrogen and Carbon Dioxide Hilic, Sacha; Boyer, Séverine A. E.; Pádua, Agílio A. H. Journal of Polymer Science Part B: Polymer Physics, Vol. 39, Issue 17 https://doi.org/10.1002/polb.1181	journal	July 2001
Aspect ratio effect of nanorod surfactants on the shape and internal morphology of block copolymer particles Ku, Kang Hee; Yang, Hyunseung; Shin, Jae Man Journal of Polymer Science Part A: Polymer Chemistry, Vol. 53, Issue 2 https://doi.org/10.1002/pola.27333	journal	August 2014
Structure–Property Relationships in CO ₂ -philic (Co)polymers: Phase Behavior, Self-Assembly, and Stabilization of Water/CO ₂ Emulsions Girard, Etienne; Tassaing, Thierry; Marty, Jean-Daniel Chemical Reviews, Vol. 116, Issue 7 https://doi.org/10.1021/acs.chemrev.5b00420	journal	March 2016
Perturbation of the Experimental Phase Diagram of a Diblock Copolymer by Blending with an Ionic Liquid Bennett, Thomas M.; Jack, Kevin S.; Thurecht, Kristofer J. Macromolecules, Vol. 49, Issue 1 https://doi.org/10.1021/acs.macromol.5b02041	journal	December 2015
High-pressure rheological analysis of CO2-induced melting point depression and viscosity reduction of poly(ε-caprolactone) Curia, S.; De Focatiis, D. S. A.; Howdle, S. M. Polymer, Vol. 69 https://doi.org/10.1016/j.polymer.2015.05.026	journal	July 2015
Morphology transition from cylindrical to lamellar microdomains of block copolymers Sakurai, Shinichi; Momii, Toshikazu; Taie, Kazuhiro Macromolecules, Vol. 26, Issue 3 https://doi.org/10.1021/ma00055a013	journal	May 1993
Mesoporous Titania Microspheres with Highly Tunable Pores as an Anode Material for Lithium Ion Batteries Fischer, Michael G.; Hua, Xiao; Wilts, Bodo D. ACS Applied Materials & Interfaces, Vol. 9, Issue 27 https://doi.org/10.1021/acsami.7b03155	journal	June 2017
A high pressure cell for supercritical CO ₂ on-line chemical reactions studied with x-ray techniques Hermida-Merino, Daniel; Portale, Giuseppe; Fields, Peter Review of Scientific Instruments, Vol. 85, Issue 9 https://doi.org/10.1063/1.4895717	journal	September 2014
How Fast Can a CRP Be Conducted with Preserved Chain End Functionality? Zhong, Mingjiang; Matyjaszewski, Krzysztof Macromolecules, Vol. 44, Issue 8 https://doi.org/10.1021/ma102834s	journal	April 2011
A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization Keddie, Daniel J. Chem. Soc. Rev., Vol. 43, Issue 2 https://doi.org/10.1039/C3CS60290G	journal	January 2014
Preparation of “Mushroom-like” Janus Particles by Site-Selective Surface-Initiated Atom Transfer Radical Polymerization in Aqueous Dispersed Systems ^† Tanaka, Takuya; Okayama, Masaru; Kitayama, Yukiya Langmuir, Vol. 26, Issue 11 https://doi.org/10.1021/la904701r	journal	June 2010
Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition Khandpur, Ashish K.; Foerster, Stephan; Bates, Frank S. Macromolecules, Vol. 28, Issue 26 https://doi.org/10.1021/ma00130a012	journal	December 1995
Clean Block Copolymer Microparticles from Supercritical CO ₂ : Universal Templates for the Facile and Scalable Fabrication of Hierarchical Mesostructured Metal Oxides Bennett, Thomas M.; He, Guping; Larder, Ryan R. Nano Letters, Vol. 18, Issue 12 https://doi.org/10.1021/acs.nanolett.8b03044	journal	November 2018
Improved Particle Size Control for the Dispersion Polymerization of Methyl methacrylate in Supercritical Carbon Dioxide McAllister, Thomas D.; Farrand, Louise D.; Howdle, Steven M. Macromolecular Chemistry and Physics, Vol. 217, Issue 20 https://doi.org/10.1002/macp.201600131	journal	June 2016
Measurement of the correlation hole in homogeneous block copolymer melts Bates, Frank S. Macromolecules, Vol. 18, Issue 3 https://doi.org/10.1021/ma00145a037	journal	May 1985
In situ small-angle X-ray scattering studies of sterically-stabilized diblock copolymer nanoparticles formed during polymerization-induced self-assembly in non-polar media Derry, Matthew J.; Fielding, Lee A.; Warren, Nicholas J. Chemical Science, Vol. 7, Issue 8 https://doi.org/10.1039/C6SC01243D	journal	January 2016
Thermally Sensitive Block Copolymer Particles Prepared via Aerosol Flow Reactor Method: Morphological Characterization and Behavior in Water Nykänen, Antti; Rahikkala, Antti; Hirvonen, Sami-Pekka Macromolecules, Vol. 45, Issue 20 https://doi.org/10.1021/ma301687b	journal	October 2012
Polymeric ionic liquids: Broadening the properties and applications of polyelectrolytes Mecerreyes, David Progress in Polymer Science, Vol. 36, Issue 12 https://doi.org/10.1016/j.progpolymsci.2011.05.007	journal	December 2011
Block Copolymer Microspheres Containing Intricate Nanometer-Sized Segregation Patterns Lu, Zhihua; Liu, Guojun; Liu, Futian Macromolecules, Vol. 34, Issue 25 https://doi.org/10.1021/ma0108463	journal	December 2001
Broad-wavelength-range chemically tunable block-copolymer photonic gels Kang, Youngjong; Walish, Joseph J.; Gorishnyy, Taras Nature Materials, Vol. 6, Issue 12 https://doi.org/10.1038/nmat2032	journal	October 2007
Biomimetic block copolymer particles with gated nanopores and ultrahigh protein sorption capacity Yu, Haizhou; Qiu, Xiaoyan; Nunes, Suzana P. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5110	journal	June 2014
Controlled Dispersion Polymerization of Methyl Methacrylate in Supercritical Carbon Dioxide via RAFT Gregory, Andrew M.; Thurecht, Kristofer J.; Howdle, Steven M. Macromolecules, Vol. 41, Issue 4 https://doi.org/10.1021/ma702017r	journal	February 2008
Optoelectronics using block copolymers Botiz, Ioan; Darling, Seth B. Materials Today, Vol. 13, Issue 5 https://doi.org/10.1016/S1369-7021(10)70083-3	journal	May 2010
Recent experiments on a small-angle/wide-angle X-ray scattering beam line at the ESRF Bras, W.; Dolbnya, I. P.; Detollenaere, D. Journal of Applied Crystallography, Vol. 36, Issue 3 https://doi.org/10.1107/S002188980300400X	journal	April 2003
Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)- block -poly(methyl methacrylate) Block Polymers for Lithography Kennemur, Justin G.; Yao, Li; Bates, Frank S. Macromolecules, Vol. 47, Issue 4 https://doi.org/10.1021/ma4020164	journal	February 2014
Frustrated Phases of Block Copolymers in Nanoparticles Higuchi, Takeshi; Tajima, Atsunori; Motoyoshi, Kiwamu Angewandte Chemie International Edition, Vol. 47, Issue 42 https://doi.org/10.1002/anie.200803003	journal	October 2008
Polymerization-Induced Self-Assembly of Block Copolymer Nano-objects via RAFT Aqueous Dispersion Polymerization Warren, Nicholas J.; Armes, Steven P. Journal of the American Chemical Society, Vol. 136, Issue 29 https://doi.org/10.1021/ja502843f	journal	July 2014
Cooperative Assembly of Block Copolymers with Deformable Interfaces: Toward Nanostructured Particles Jeon, Seog-Jin; Yi, Gi-Ra; Yang, Seung-Man Advanced Materials, Vol. 20, Issue 21 https://doi.org/10.1002/adma.200801377	journal	November 2008
Polymer synthesis and processing using supercritical carbon dioxide Cooper, Andrew I. Journal of Materials Chemistry, Vol. 10, Issue 2 https://doi.org/10.1039/a906486i	journal	January 2000
Particle Size Distribution Inferred from Small-Angle X-ray Scattering and Transmission Electron Microscopy Rieker, Thomas; Hanprasopwattana, Aree; Datye, Abhaya Langmuir, Vol. 15, Issue 2 https://doi.org/10.1021/la9810713	journal	January 1999
Polymer self assembly in semiconductor microelectronics Black, C. T.; Ruiz, R.; Breyta, G. IBM Journal of Research and Development, Vol. 51, Issue 5 https://doi.org/10.1147/rd.515.0605	journal	September 2007
A facile route to bespoke macro- and mesoporous block copolymer microparticles He, Guping; Bennett, Thomas M.; Alauhdin, Mohammad Polymer Chemistry, Vol. 9, Issue 27 https://doi.org/10.1039/C8PY00707A	journal	January 2018
Frustrated Phases of Block Copolymers in Nanoparticles Higuchi, Takeshi; Tajima, Atsunori; Motoyoshi, Kiwamu Angewandte Chemie, Vol. 120, Issue 42 https://doi.org/10.1002/ange.200803003	journal	October 2008

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