Designing Macromolecules on Nanoparticle Surfaces: In Situ Formation of Silica Grafted with Star Chains

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dc.contributor.authorAldakheel, Fatimah
dc.contributor.authorNtetsikas, Konstantinos
dc.contributor.authorYudhanto, Arief
dc.contributor.authorLubineau, Gilles
dc.contributor.authorHadjichristidis, Nikos
dc.contributor.departmentPolymer Synthesis Laboratory, Chemistry Program, KAUST Catalysis Center, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia
dc.contributor.departmentMechanics of Composites for Energy and Mobility Laboratory, Mechanical Engineering Program, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
dc.contributor.departmentChemical Science Program
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentMechanical Engineering Program
dc.date.accessioned2023-11-20T05:34:39Z
dc.date.available2023-11-20T05:34:39Z
dc.date.issued2023-11-17
dc.description.abstractHerein, we report the synthesis and characterization of asymmetric 3-arm homostar (3h-star) and 3-miktoarm star (3μ-star) chains grafted on silica nanoparticles simultaneously with the formation of silica. We employed high-vacuum anionic polymerization techniques to synthesize well-defined ω-triethoxysilyl (TEOS)-terminated (PS)2PS, (PS)2PI, and (PS)2PI-b-PS macromonomers (polystyrene (PS) and polyisoprene (PI)), which upon hydrolysis/condensation of the terminal TEOS yielded the grafted silica nanoparticles. The molecular characteristics of the precursors (PS)2PS-TEOS, (PS)2PI-TEOS, and (PS)2PI-b-PS-TEOS were determined by proton nuclear magnetic resonance (NMR) spectroscopy and size-exclusion chromatography (SEC). The formation of 3h-star and 3μ-star@SiO2 nanoparticles was demonstrated by Fourier transform infrared spectroscopy, 29Si solid-state NMR, transmission electron microscopy, thermogravimetry, and dynamic light scattering. Blends of 3h-star and 3μ-star@SiO2 with a thermoplastic elastomer (TPE) (PS-b-PI-b-PS), synthesized by anionic polymerization, were obtained by the evaporation of solutions containing the TPE and the grafted nanoparticles. The role of 3h-star and 3μ-star@SiO2 in the mechanical properties and morphological features of the polymer matrices was examined by tensile testing and scanning electron microscopy. This synthetic methodology controls the molecular characteristics, particle size, and grafting density of nanoparticles and enhances the mechanical properties of the final nanocomposites.
dc.description.sponsorshipThis research was completely supported by King Abdullah University of Science and Technology (KAUST). The authors thank Valentina Musteata from the Advanced Imaging and Characterization Laboratories at KAUST for providing TEM and STEM-EDX imaging.
dc.eprint.versionPost-print
dc.identifier.doi10.1021/acsapm.3c01246
dc.identifier.issn2637-6105
dc.identifier.issn2637-6105
dc.identifier.journalACS Applied Polymer Materials
dc.identifier.urihttps://repository.kaust.edu.sa/handle/10754/695653
dc.publisherAmerican Chemical Society (ACS)
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Polymer Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see .
dc.rights.embargodate2024-11-17
dc.titleDesigning Macromolecules on Nanoparticle Surfaces: In Situ Formation of Silica Grafted with Star Chains
dc.typeArticle
display.details.left<span><h5>Embargo End Date</h5>2024-11-17<br><br><h5>Type</h5>Article<br><br><h5>Authors</h5><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0001-6368-4655&spc.sf=dc.date.issued&spc.sd=DESC">Aldakheel, Fatimah</a> <a href="https://orcid.org/0000-0001-6368-4655" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-9236-931X&spc.sf=dc.date.issued&spc.sd=DESC">Ntetsikas, Konstantinos</a> <a href="https://orcid.org/0000-0002-9236-931X" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-8839-415X&spc.sf=dc.date.issued&spc.sd=DESC">Yudhanto, Arief</a> <a href="https://orcid.org/0000-0002-8839-415X" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-7370-6093&spc.sf=dc.date.issued&spc.sd=DESC">Lubineau, Gilles</a> <a href="https://orcid.org/0000-0002-7370-6093" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0003-1442-1714&spc.sf=dc.date.issued&spc.sd=DESC">Hadjichristidis, Nikos</a> <a href="https://orcid.org/0000-0003-1442-1714" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><br><h5>KAUST Department</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Polymer Synthesis Laboratory, Chemistry Program, KAUST Catalysis Center, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia,equals">Polymer Synthesis Laboratory, Chemistry Program, KAUST Catalysis Center, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Mechanics of Composites for Energy and Mobility Laboratory, Mechanical Engineering Program, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia,equals">Mechanics of Composites for Energy and Mobility Laboratory, Mechanical Engineering Program, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Chemical Science Program,equals">Chemical Science Program</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Physical Science and Engineering (PSE) Division,equals">Physical Science and Engineering (PSE) Division</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=KAUST Catalysis Center (KCC),equals">KAUST Catalysis Center (KCC)</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Mechanical Engineering Program,equals">Mechanical Engineering Program</a><br><br><h5>Date</h5>2023-11-17</span>
display.details.right<span><h5>Abstract</h5>Herein, we report the synthesis and characterization of asymmetric 3-arm homostar (3h-star) and 3-miktoarm star (3μ-star) chains grafted on silica nanoparticles simultaneously with the formation of silica. We employed high-vacuum anionic polymerization techniques to synthesize well-defined ω-triethoxysilyl (TEOS)-terminated (PS)2PS, (PS)2PI, and (PS)2PI-b-PS macromonomers (polystyrene (PS) and polyisoprene (PI)), which upon hydrolysis/condensation of the terminal TEOS yielded the grafted silica nanoparticles. The molecular characteristics of the precursors (PS)2PS-TEOS, (PS)2PI-TEOS, and (PS)2PI-b-PS-TEOS were determined by proton nuclear magnetic resonance (NMR) spectroscopy and size-exclusion chromatography (SEC). The formation of 3h-star and 3μ-star@SiO2 nanoparticles was demonstrated by Fourier transform infrared spectroscopy, 29Si solid-state NMR, transmission electron microscopy, thermogravimetry, and dynamic light scattering. Blends of 3h-star and 3μ-star@SiO2 with a thermoplastic elastomer (TPE) (PS-b-PI-b-PS), synthesized by anionic polymerization, were obtained by the evaporation of solutions containing the TPE and the grafted nanoparticles. The role of 3h-star and 3μ-star@SiO2 in the mechanical properties and morphological features of the polymer matrices was examined by tensile testing and scanning electron microscopy. This synthetic methodology controls the molecular characteristics, particle size, and grafting density of nanoparticles and enhances the mechanical properties of the final nanocomposites.<br><br><h5>Acknowledgements</h5>This research was completely supported by King Abdullah University of Science and Technology (KAUST). The authors thank Valentina Musteata from the Advanced Imaging and Characterization Laboratories at KAUST for providing TEM and STEM-EDX imaging.<br><br><h5>Publisher</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.publisher=American Chemical Society (ACS),equals">American Chemical Society (ACS)</a><br><br><h5>Journal</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.journal=ACS Applied Polymer Materials,equals">ACS Applied Polymer Materials</a><br><br><h5>DOI</h5><a href="https://doi.org/10.1021/acsapm.3c01246">10.1021/acsapm.3c01246</a></span>
kaust.acknowledged.supportUnitAdvanced Imaging and Characterization Laboratories
kaust.personAldakheel, Fatimah
kaust.personNtetsikas, Konstantinos
kaust.personYudhanto, Arief
kaust.personLubineau, Gilles
kaust.personHadjichristidis, Nikos
orcid.authorAldakheel, Fatimah::0000-0001-6368-4655
orcid.authorNtetsikas, Konstantinos::0000-0002-9236-931X
orcid.authorYudhanto, Arief::0000-0002-8839-415X
orcid.authorLubineau, Gilles::0000-0002-7370-6093
orcid.authorHadjichristidis, Nikos::0000-0003-1442-1714
orcid.id0000-0003-1442-1714
orcid.id0000-0002-7370-6093
orcid.id0000-0002-8839-415X
orcid.id0000-0002-9236-931X
orcid.id0000-0001-6368-4655
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