Distribution of Chains in Polymer Brushes Produced by a “Grafting From” Mechanism

Martinez, Andre P.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.; Adamson, Douglas H.

doi:10.1021/acs.macromol.5b02261

Title: Distribution of Chains in Polymer Brushes Produced by a “Grafting From” Mechanism

Journal Article · Mon Jan 11 00:00:00 EST 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.5b02261· OSTI ID:1261508

Martinez, Andre P. ^[1]; Carrillo, Jan-Michael Y. ^[2]; Dobrynin, Andrey V. ^[3]; Adamson, Douglas H. ^[1]

Univ. of Connecticut, Storrs, CT (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Akron, OH (United States)

The molecular weight and polydispersity of the chains in a polymer brush are critical parameters determining the brush properties. However, the characterization of polymer brushes is hindered by the vanishingly small mass of polymer present in brush layers. In this study, in order to obtain sufficient quantities of polymer for analysis, polymer brushes were grown from high surface area fibrous nylon membranes by ATRP. We synthesized the brushes with varying surface initiator densities, polymerization times, and amounts of sacrificial initiator, then cleaved from the substrate, and analyzed by GPC and NMR. Characterization showed that the surface-grown polymer chains were more polydisperse and had lower average molecular weight compared to solution-grown polymers synthesized concurrently. Furthermore, the molecular weight distribution of the polymer brushes was observed to be bimodal, with a low molecular weight population of chains representing a significant mass fraction of the polymer chains at high surface initiator densities. Moreover, the origin of this low MW polymer fraction is proposed to be the termination of growing chains by recombination during the early stages of polymerization, a mechanism confirmed by molecular dynamics simulations of brush polymerization.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; CHE-1310453; DMR-1004576

OSTI ID:: 1261508

Journal Information:: Macromolecules, Vol. 49, Issue 2; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 30 works

Citation information provided by
Web of Science

References (30)

Protein—surface interactions in the presence of polyethylene oxide Jeon, S. I.; Lee, J. H.; Andrade, J. D. Journal of Colloid and Interface Science, Vol. 142, Issue 1 https://doi.org/10.1016/0021-9797(91)90043-8	journal	March 1991
Protein Adsorption on Oligo(ethylene glycol)-Terminated Alkanethiolate Self-Assembled Monolayers: The Molecular Basis for Nonfouling Behavior Li, Lingyan; Chen, Shengfu; Zheng, Jie The Journal of Physical Chemistry B, Vol. 109, Issue 7 https://doi.org/10.1021/jp0473321	journal	February 2005
Tailoring of surfaces with ultrathin polymer films for survival and growth of neurons in culture Rühe, Jürgen; Yano, Ryoji; Lee, Jae-Suk Journal of Biomaterials Science, Polymer Edition, Vol. 10, Issue 8 https://doi.org/10.1163/156856299X00928	journal	January 1999
RGD modified polymers: biomaterials for stimulated cell adhesion and beyond Hersel, Ulrich; Dahmen, Claudia; Kessler, Horst Biomaterials, Vol. 24, Issue 24 https://doi.org/10.1016/S0142-9612(03)00343-0	journal	November 2003
Tribological Properties of Poly(methyl methacrylate) Brushes Prepared by Surface-Initiated Atom Transfer Radical Polymerization Sakata, Hiroki; Kobayashi, Motoyasu; Otsuka, Hideyuki Polymer Journal, Vol. 37, Issue 10 https://doi.org/10.1295/polymj.37.767	journal	October 2005
Friction behavior of high-density poly(2-methacryloyloxyethyl phosphorylcholine) brush in aqueous media Kobayashi, Motoyasu; Terayama, Yuki; Hosaka, Nao Soft Matter, Vol. 3, Issue 6 https://doi.org/10.1039/b615780g	journal	January 2007
Self-Organization of Nanocrystals in Polymer Brushes. Application in Heterojunction Photovoltaic Diodes Snaith, Henry J.; Whiting, Gregory L.; Sun, Baoquan Nano Letters, Vol. 5, Issue 9 https://doi.org/10.1021/nl0505039	journal	September 2005
Grafting of poly(3-hexylthiophene) brushes on oxides using click chemistry Paoprasert, Peerasak; Spalenka, Josef W.; Peterson, Dane L. J. Mater. Chem., Vol. 20, Issue 13 https://doi.org/10.1039/B920233A	journal	January 2010
Polymer-Grafted-Nanoparticle Surfactants Maillard, Damien; Kumar, Sanat K.; Rungta, Atri Nano Letters, Vol. 11, Issue 11 https://doi.org/10.1021/nl202651u	journal	November 2011
Surface-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization from Fine Particles Functionalized with Trithiocarbonates Ohno, Kohji; Ma, Ying; Huang, Yun Macromolecules, Vol. 44, Issue 22 https://doi.org/10.1021/ma202105y	journal	November 2011
Stimuli-responsive molecular brushes Lee, Hyung-il; Pietrasik, Joanna; Sheiko, Sergei S. Progress in Polymer Science, Vol. 35, Issue 1-2 https://doi.org/10.1016/j.progpolymsci.2009.11.002	journal	January 2010
Polymer Brushes via Surface-Initiated Controlled Radical Polymerization: Synthesis, Characterization, Properties, and Applications Barbey, Raphael; Lavanant, Laurent; Paripovic, Dusko Chemical Reviews, Vol. 109, Issue 11 https://doi.org/10.1021/cr900045a	journal	November 2009
Polymer Brushes Milner, S. T. Science, Vol. 251, Issue 4996 https://doi.org/10.1126/science.251.4996.905	journal	February 1991
Reduction of frictional forces between solid surfaces bearing polymer brushes Klein, Jacob; Kumacheva, Eugenia; Mahalu, Diana Nature, Vol. 370, Issue 6491 https://doi.org/10.1038/370634a0	journal	August 1994
Synthesis of Polystyrene Brushes on Silicate Substrates via Carbocationic Polymerization from Self-Assembled Monolayers Zhao, Bin; Brittain, William J. Macromolecules, Vol. 33, Issue 2 https://doi.org/10.1021/ma9910181	journal	January 2000
Surface-Initiated Anionic Polymerization of Styrene by Means of Self-Assembled Monolayers Jordan, Rainer; Ulman, Abraham; Kang, Jung F. Journal of the American Chemical Society, Vol. 121, Issue 5 https://doi.org/10.1021/ja981348l	journal	February 1999
Ring-Opening Metathesis Polymerization from Surfaces Weck, Marcus; Jackiw, Jennifer J.; Rossi, Robert R. Journal of the American Chemical Society, Vol. 121, Issue 16 https://doi.org/10.1021/ja983297y	journal	April 1999
Radical grafting from glass fiber surface: Graft polymerization of vinyl monomers initiated by azo groups introduced onto the surface Fujiki, Kazuhiro; Sakamoto, Munenori; Yoshida, Akira Journal of Polymer Science Part A: Polymer Chemistry, Vol. 37, Issue 13 https://doi.org/10.1002/(SICI)1099-0518(19990701)37:13<2121::AID-POLA27>3.3.CO;2-5	journal	July 1999
Polymer brushes here, there, and everywhere: Recent advances in their practical applications and emerging opportunities in multiple research fields Azzaroni, Omar Journal of Polymer Science Part A: Polymer Chemistry, Vol. 50, Issue 16 https://doi.org/10.1002/pola.26119	journal	May 2012
Surface-initiated atom transfer radical polymerization of methyl methacrylate on magnetite nanoparticles Marutani, Eizo; Yamamoto, Shinpei; Ninjbadgar, Tsedev Polymer, Vol. 45, Issue 7 https://doi.org/10.1016/j.polymer.2004.02.005	journal	March 2004
Effect of Substrate Geometry on Polymer Molecular Weight and Polydispersity during Surface-Initiated Polymerization Gorman, Christopher B.; Petrie, Randall J.; Genzer, Jan Macromolecules, Vol. 41, Issue 13 https://doi.org/10.1021/ma8004857	journal	June 2008
Kinetics of surface-initiated atom transfer radical polymerization Kim, Jong-Bum; Huang, Wenxi; Miller, Matthew D. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 41, Issue 3 https://doi.org/10.1002/pola.10568	journal	December 2002
On-Demand Degrafting and the Study of Molecular Weight and Grafting Density of Poly(methyl methacrylate) Brushes on Flat Silica Substrates Patil, Rohan R.; Turgman-Cohen, Salomon; Šrogl, Jiří Langmuir, Vol. 31, Issue 8 https://doi.org/10.1021/la5044766	journal	February 2015
Simultaneous Bulk- and Surface-Initiated Controlled Radical Polymerization from Planar Substrates Turgman-Cohen, Salomon; Genzer, Jan Journal of the American Chemical Society, Vol. 133, Issue 44 https://doi.org/10.1021/ja2081636	journal	November 2011
Formation and equilibrium properties of living polymer brushes Milchev, A.; Wittmer, J. P.; Landau, D. P. The Journal of Chemical Physics, Vol. 112, Issue 3 https://doi.org/10.1063/1.480600	journal	January 2000
Polymers at Interfaces: Using Atom Transfer Radical Polymerization in the Controlled Growth of Homopolymers and Block Copolymers from Silicon Surfaces in the Absence of Untethered Sacrificial Initiator Matyjaszewski, Krzysztof; Miller, Peter J.; Shukla, Nisha Macromolecules, Vol. 32, Issue 26 https://doi.org/10.1021/ma991146p	journal	December 1999
Functionalization of Surfaces by Water-Accelerated Atom-Transfer Radical Polymerization of Hydroxyethyl Methacrylate and Subsequent Derivatization Huang, Wenxi; Kim, Jong-Bum; Bruening, Merlin L. Macromolecules, Vol. 35, Issue 4 https://doi.org/10.1021/ma011159e	journal	February 2002
Functionalization of Nylon Membranes via Surface-Initiated Atom-Transfer Radical Polymerization Xu, F. J.; Zhao, J. P.; Kang, E. T. Langmuir, Vol. 23, Issue 16 https://doi.org/10.1021/la7011342	journal	July 2007
Initiation Efficiency in the Synthesis of Molecular Brushes by Grafting from via Atom Transfer Radical Polymerization Sumerlin, Brent S.; Neugebauer, Dorota; Matyjaszewski, Krzysztof Macromolecules, Vol. 38, Issue 3 https://doi.org/10.1021/ma048351b	journal	February 2005
Miscibility and hydrolytic degradation in alkaline solution of poly(l-lactide) and poly(methyl methacrylate) blends Shirahase, Tomoko; Komatsu, Yoichi; Tominaga, Yoichi Polymer, Vol. 47, Issue 13 https://doi.org/10.1016/j.polymer.2006.04.012	journal	June 2006

Cited By (7)

Optimisation of grafting of low fouling polymers from three-dimensional scaffolds via surface-initiated Cu(0) mediated polymerisation Duque-Sánchez, Lina; Brack, Narelle; Postma, Almar Journal of Materials Chemistry B, Vol. 6, Issue 37 https://doi.org/10.1039/c8tb01828f	journal	January 2018
Controlled Growth of Ultra‐Thick Polymer Brushes via Surface‐Initiated Atom Transfer Radical Polymerization with Active Polymers as Initiators Zeng, Yiyang; Xie, Lei; Chi, Fangting Macromolecular Rapid Communications https://doi.org/10.1002/marc.201900078	journal	April 2019
Grafting density dominant glass transition of dry polystyrene brushes Zuo, Biao; Zhang, Shasha; Niu, Chen Soft Matter, Vol. 13, Issue 13 https://doi.org/10.1039/c6sm02790c	journal	January 2017
Synthesis and characterization of silica-polyvinyl imidazole core-shell nanoparticles via combination of RAFT polymerization and grafting-to method: Silica-Polyvinyl Imidazole Core-Shell Nanoparticles Gargari, Jafar Ettehadi; Shakeri, Alireza; Kalal, Hossein Sid Polymers for Advanced Technologies, Vol. 28, Issue 12 https://doi.org/10.1002/pat.4077	journal	May 2017
Controlled and tunable design of polymer interface for immobilization of enzymes: does curvature matter? Marschelke, Claudia; Raguzin, Ivan; Matura, Anke Soft Matter, Vol. 13, Issue 5 https://doi.org/10.1039/c6sm02380k	journal	January 2017
Gold nanoparticle distribution in polyelectrolyte brushes loaded at different pH conditions Boyaciyan, Dikran; Braun, Larissa; Löhmann, Oliver The Journal of Chemical Physics, Vol. 149, Issue 16 https://doi.org/10.1063/1.5035554	journal	October 2018
Thermoresponsive Brushes Facilitate Effective Reinforcement of Calcium Phosphate Cements Petre, Daniela-Geta; Nadar, Robin; Tu, Yingfeng ACS Applied Materials & Interfaces, Vol. 11, Issue 30 https://doi.org/10.1021/acsami.9b08311	journal	June 2019

Similar Records

Tuning dispersity of linear polymers and polymeric brushes grown from nanoparticles by atom transfer radical polymerization

Journal Article · Wed Oct 13 00:00:00 EDT 2021 · Polymer Chemistry · OSTI ID:1261508

Yin, Rongguan; Wang, Zongyu; Bockstaller, Michael R.; +1 more

Temperature-dependent conformational change of PNIPAM grafted chains at high surface density in water.

Journal Article · Tue Jul 01 00:00:00 EDT 2003 · Proposed for publication in Macromolecules. · OSTI ID:1261508

Satija, Sushil K; Mendez, Sergio; Balamurugan, Sreelatha S; +4 more

Degradable cellulose‐based polymer brushes with controlled grafting densities

Journal Article · Thu Aug 29 00:00:00 EDT 2019 · Journal of Polymer Science. Part A, Polymer Chemistry · OSTI ID:1261508

Olszewski, Mateusz; Li, Lingchun; Xie, Guojun; +3 more

Related Subjects

36 MATERIALS SCIENCE

Title: Distribution of Chains in Polymer Brushes Produced by a “Grafting From” Mechanism

Citation Formats

References (30)

Cited By (7)

Similar Records

Related Subjects