Functionalization of single-walled carbon nanotubes with end-capped polystyrene via a single-step diels–alder cycloaddition

Maria Malvina Stathouraki; Christos Pantazidis; Emmanouil Mygiakis; Apostolos Avgeropoulos; Georgios Sakellariou

doi:10.3390/polym13071169

Functionalization of single-walled carbon nanotubes with end-capped polystyrene via a single-step diels–alder cycloaddition

Maria Malvina Stathouraki
, Christos Pantazidis
, Emmanouil Mygiakis
, Apostolos Avgeropoulos
, Georgios Sakellariou (Corresponding author)

Research output: Contribution to journal › Article › Academic › peer-review

8 Citations (Scopus)

Abstract

A facile, single-step, [4+2] Diels–Alder cycloaddition reaction for the surface functionaliza-tion of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (~230^◦ C) without any catalyst between the sp² network of carbon nanotubes, which acted as dienophile, and the diphenylethy-lene cyclobutene (DPE-CB) terminal group of the polystyrene chain. Anionic polymerization was employed for the synthesis of the polystyrene macromolecule, and successful and quantitative end-capping reaction with the DPE-CB molecule was confirmed by matrix-assisted laser desorp-tion/ionization time of flight mass spectroscopy. Thermogravimetric analysis revealed the wt % of the grafted macromolecule on the CNT surface as well as the grafting density of the polymer chains on the SWNTs (0.027 chains nm⁻²). Direct evidence for the surface functionalization and the presence of thin polystyrene film was obtained by transmission electron microscopy (TEM) and by atomic force microscopy (AFM).

Original language	English
Article number	1169
Number of pages	12
Journal	Polymers
Volume	13
Issue number	7
DOIs	https://doi.org/10.3390/polym13071169
Publication status	Published - 1 Apr 2021
Externally published	Yes

Bibliographical note

Funding Information:
Supplementary Materials: The followi1ng are available online at https://www.mdpi.com/article/10 .3390/polym13071169/s1, Figure S1. 1H-NMR spectrum of DPE-CB. Author Contributions: G.S. was responsible for this work and the design of the experiments. M.-M.S. Synthesized and characterized the end-functionalized polystyrene. C.P., and E.M. synthesized and characterized the SWNTs-g-PS. A.A. characterized the SWNTs-g-PS via TEM and AFM. All characterized the SWNTs-g-PS. A.A. characterized the SWNTs-g-PS via TEM and AFM. All authors have read and agreed to the published version of the manuscript. Funding: This research was co-financed by the European Union and Greek national funds through the Operational Program Competitiveness and innovation, under the call RESEARCH–CREATE– the Operational Program Competitiveness and innovation, under the call RESEARCH–CREATE– INNOVATE (project code: T1E∆K-02576). Institutional Review Board Statement: Not applicable. Institutional Review Board Statement: Not applicable. Informed Consent Statement: Not applicable. Informed Consent Statement: Not applicable. Data Availability Statement: The data presented in this study are available in this manuscript and Dthaet aSAupvpailleambeilnittyarSyt Iantefomrmenatt:ioTnh eSedcattiaonp.r esented in this study are available in this manuscript and the Supplementary Information Section. Acknowledgments: This research was co-financed by the European Union and Greek national Afuckndnso wthlerdougmghe nthtse: TOhpiserreastieoanrcahl wPraosgcroa-mfin aCnocmedpbetyittihveenEeusrso paenadn Uinnnioovnaatinodn,G ruenedkenrattihoen aclaflul nRdEs-tShEroAuRgChHth–eCROEpAerTaEti–oInNaNl OPrVoAgrTaEm (pCroomjecptectoitdivee: nΤe1sΕsΔaΚn-d02i5n7n6o)v. ation, under the call RESEARCH– CCRoEnAflTicEt–sI oNfN InOtVerAeTstE: T(phreoajeuctthcoordse d: eTc1laEr∆eK n-o02c5o7n6f)l.ict of interest.

Funding

Supplementary Materials: The followi1ng are available online at https://www.mdpi.com/article/10 .3390/polym13071169/s1, Figure S1. 1H-NMR spectrum of DPE-CB. Author Contributions: G.S. was responsible for this work and the design of the experiments. M.-M.S. Synthesized and characterized the end-functionalized polystyrene. C.P., and E.M. synthesized and characterized the SWNTs-g-PS. A.A. characterized the SWNTs-g-PS via TEM and AFM. All characterized the SWNTs-g-PS. A.A. characterized the SWNTs-g-PS via TEM and AFM. All authors have read and agreed to the published version of the manuscript. Funding: This research was co-financed by the European Union and Greek national funds through the Operational Program Competitiveness and innovation, under the call RESEARCH–CREATE– the Operational Program Competitiveness and innovation, under the call RESEARCH–CREATE– INNOVATE (project code: T1E∆K-02576). Institutional Review Board Statement: Not applicable. Institutional Review Board Statement: Not applicable. Informed Consent Statement: Not applicable. Informed Consent Statement: Not applicable. Data Availability Statement: The data presented in this study are available in this manuscript and Dthaet aSAupvpailleambeilnittyarSyt Iantefomrmenatt:ioTnh eSedcattiaonp.r esented in this study are available in this manuscript and the Supplementary Information Section. Acknowledgments: This research was co-financed by the European Union and Greek national Afuckndnso wthlerdougmghe nthtse: TOhpiserreastieoanrcahl wPraosgcroa-mfin aCnocmedpbetyittihveenEeusrso paenadn Uinnnioovnaatinodn,G ruenedkenrattihoen aclaflul nRdEs-tShEroAuRgChHth–eCROEpAerTaEti–oInNaNl OPrVoAgrTaEm (pCroomjecptectoitdivee: nΤe1sΕsΔaΚn-d02i5n7n6o)v. ation, under the call RESEARCH– CCRoEnAflTicEt–sI oNfN InOtVerAeTstE: T(phreoajeuctthcoordse d: eTc1laEr∆eK n-o02c5o7n6f)l.ict of interest.

Keywords

Anionic polymerization
Single-walled carbon nanotubes
Surface functionaliza-tion
[4+2] Diels–Alder cycloaddition

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10.3390/polym13071169

Cite this

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title = "Functionalization of single-walled carbon nanotubes with end-capped polystyrene via a single-step diels–alder cycloaddition",

abstract = "A facile, single-step, [4+2] Diels–Alder cycloaddition reaction for the surface functionaliza-tion of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (\textasciitilde{}230◦ C) without any catalyst between the sp2 network of carbon nanotubes, which acted as dienophile, and the diphenylethy-lene cyclobutene (DPE-CB) terminal group of the polystyrene chain. Anionic polymerization was employed for the synthesis of the polystyrene macromolecule, and successful and quantitative end-capping reaction with the DPE-CB molecule was confirmed by matrix-assisted laser desorp-tion/ionization time of flight mass spectroscopy. Thermogravimetric analysis revealed the wt \% of the grafted macromolecule on the CNT surface as well as the grafting density of the polymer chains on the SWNTs (0.027 chains nm−2). Direct evidence for the surface functionalization and the presence of thin polystyrene film was obtained by transmission electron microscopy (TEM) and by atomic force microscopy (AFM).",

keywords = "Anionic polymerization, Single-walled carbon nanotubes, Surface functionaliza-tion, [4+2] Diels–Alder cycloaddition",

author = "Stathouraki, \{Maria Malvina\} and Christos Pantazidis and Emmanouil Mygiakis and Apostolos Avgeropoulos and Georgios Sakellariou",

note = "Funding Information: Supplementary Materials: The followi1ng are available online at https://www.mdpi.com/article/10 .3390/polym13071169/s1, Figure S1. 1H-NMR spectrum of DPE-CB. Author Contributions: G.S. was responsible for this work and the design of the experiments. M.-M.S. Synthesized and characterized the end-functionalized polystyrene. C.P., and E.M. synthesized and characterized the SWNTs-g-PS. A.A. characterized the SWNTs-g-PS via TEM and AFM. All characterized the SWNTs-g-PS. A.A. characterized the SWNTs-g-PS via TEM and AFM. All authors have read and agreed to the published version of the manuscript. Funding: This research was co-financed by the European Union and Greek national funds through the Operational Program Competitiveness and innovation, under the call RESEARCH–CREATE– the Operational Program Competitiveness and innovation, under the call RESEARCH–CREATE– INNOVATE (project code: T1E∆K-02576). Institutional Review Board Statement: Not applicable. Institutional Review Board Statement: Not applicable. Informed Consent Statement: Not applicable. Informed Consent Statement: Not applicable. Data Availability Statement: The data presented in this study are available in this manuscript and Dthaet aSAupvpailleambeilnittyarSyt Iantefomrmenatt:ioTnh eSedcattiaonp.r esented in this study are available in this manuscript and the Supplementary Information Section. Acknowledgments: This research was co-financed by the European Union and Greek national Afuckndnso wthlerdougmghe nthtse: TOhpiserreastieoanrcahl wPraosgcroa-mfin aCnocmedpbetyittihveenEeusrso paenadn Uinnnioovnaatinodn,G ruenedkenrattihoen aclaflul nRdEs-tShEroAuRgChHth–eCROEpAerTaEti–oInNaNl OPrVoAgrTaEm (pCroomjecptectoitdivee: nΤe1sΕsΔaΚn-d02i5n7n6o)v. ation, under the call RESEARCH– CCRoEnAflTicEt–sI oNfN InOtVerAeTstE: T(phreoajeuctthcoordse d: eTc1laEr∆eK n-o02c5o7n6f)l.ict of interest. ",

year = "2021",

month = apr,

day = "1",

doi = "10.3390/polym13071169",

language = "English",

volume = "13",

journal = "Polymers",

issn = "2073-4360",

publisher = "Multidisciplinary Digital Publishing Institute (MDPI)",

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T1 - Functionalization of single-walled carbon nanotubes with end-capped polystyrene via a single-step diels–alder cycloaddition

AU - Stathouraki, Maria Malvina

AU - Pantazidis, Christos

AU - Mygiakis, Emmanouil

AU - Avgeropoulos, Apostolos

AU - Sakellariou, Georgios

N1 - Funding Information: Supplementary Materials: The followi1ng are available online at https://www.mdpi.com/article/10 .3390/polym13071169/s1, Figure S1. 1H-NMR spectrum of DPE-CB. Author Contributions: G.S. was responsible for this work and the design of the experiments. M.-M.S. Synthesized and characterized the end-functionalized polystyrene. C.P., and E.M. synthesized and characterized the SWNTs-g-PS. A.A. characterized the SWNTs-g-PS via TEM and AFM. All characterized the SWNTs-g-PS. A.A. characterized the SWNTs-g-PS via TEM and AFM. All authors have read and agreed to the published version of the manuscript. Funding: This research was co-financed by the European Union and Greek national funds through the Operational Program Competitiveness and innovation, under the call RESEARCH–CREATE– the Operational Program Competitiveness and innovation, under the call RESEARCH–CREATE– INNOVATE (project code: T1E∆K-02576). Institutional Review Board Statement: Not applicable. Institutional Review Board Statement: Not applicable. Informed Consent Statement: Not applicable. Informed Consent Statement: Not applicable. Data Availability Statement: The data presented in this study are available in this manuscript and Dthaet aSAupvpailleambeilnittyarSyt Iantefomrmenatt:ioTnh eSedcattiaonp.r esented in this study are available in this manuscript and the Supplementary Information Section. Acknowledgments: This research was co-financed by the European Union and Greek national Afuckndnso wthlerdougmghe nthtse: TOhpiserreastieoanrcahl wPraosgcroa-mfin aCnocmedpbetyittihveenEeusrso paenadn Uinnnioovnaatinodn,G ruenedkenrattihoen aclaflul nRdEs-tShEroAuRgChHth–eCROEpAerTaEti–oInNaNl OPrVoAgrTaEm (pCroomjecptectoitdivee: nΤe1sΕsΔaΚn-d02i5n7n6o)v. ation, under the call RESEARCH– CCRoEnAflTicEt–sI oNfN InOtVerAeTstE: T(phreoajeuctthcoordse d: eTc1laEr∆eK n-o02c5o7n6f)l.ict of interest.

PY - 2021/4/1

Y1 - 2021/4/1

N2 - A facile, single-step, [4+2] Diels–Alder cycloaddition reaction for the surface functionaliza-tion of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (~230◦ C) without any catalyst between the sp2 network of carbon nanotubes, which acted as dienophile, and the diphenylethy-lene cyclobutene (DPE-CB) terminal group of the polystyrene chain. Anionic polymerization was employed for the synthesis of the polystyrene macromolecule, and successful and quantitative end-capping reaction with the DPE-CB molecule was confirmed by matrix-assisted laser desorp-tion/ionization time of flight mass spectroscopy. Thermogravimetric analysis revealed the wt % of the grafted macromolecule on the CNT surface as well as the grafting density of the polymer chains on the SWNTs (0.027 chains nm−2). Direct evidence for the surface functionalization and the presence of thin polystyrene film was obtained by transmission electron microscopy (TEM) and by atomic force microscopy (AFM).

AB - A facile, single-step, [4+2] Diels–Alder cycloaddition reaction for the surface functionaliza-tion of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (~230◦ C) without any catalyst between the sp2 network of carbon nanotubes, which acted as dienophile, and the diphenylethy-lene cyclobutene (DPE-CB) terminal group of the polystyrene chain. Anionic polymerization was employed for the synthesis of the polystyrene macromolecule, and successful and quantitative end-capping reaction with the DPE-CB molecule was confirmed by matrix-assisted laser desorp-tion/ionization time of flight mass spectroscopy. Thermogravimetric analysis revealed the wt % of the grafted macromolecule on the CNT surface as well as the grafting density of the polymer chains on the SWNTs (0.027 chains nm−2). Direct evidence for the surface functionalization and the presence of thin polystyrene film was obtained by transmission electron microscopy (TEM) and by atomic force microscopy (AFM).

KW - Anionic polymerization

KW - Single-walled carbon nanotubes

KW - Surface functionaliza-tion

KW - [4+2] Diels–Alder cycloaddition

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DO - 10.3390/polym13071169

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AN - SCOPUS:85104185443

SN - 2073-4360

VL - 13

JO - Polymers

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M1 - 1169

ER -

Functionalization of single-walled carbon nanotubes with end-capped polystyrene via a single-step diels–alder cycloaddition

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Keywords

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