Post-Polymerization Modification of Fluoropolymers via UV Irradiation in the Presence of a Photoacid Generator

Anastasia Nika; Christina Gkioka; Fotini Machairioti; Panagiotis Bilalis; Jiaxi Xu; Katarzyna Gajos; Kamil Awsiuk; Panagiota Petrou; Margarita Chatzichristidi

doi:10.3390/polym15030493

Post-Polymerization Modification of Fluoropolymers via UV Irradiation in the Presence of a Photoacid Generator

Anastasia Nika, Christina Gkioka, Fotini Machairioti, Panagiotis Bilalis, Jiaxi Xu, Katarzyna Gajos, Kamil Awsiuk, Panagiota Petrou, Margarita Chatzichristidi

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

Abstract

Fluorinated polymers have unique wettability and protein adsorption properties. The site-specific alteration of these properties could expand their application to different research areas. In this work, a fluorinated homopolymer and two of its copolymers with 4-vinylbenzyl glycidyl ether (VBGE) are synthesized by free radical polymerization. The produced polymers are then used to develop resist formulations by the addition of a photoacid generator. Films of these formulations are exposed to ultraviolet radiation through a binary mask and heated to create the pattern. It is found that the water contact angle values of the exposed films areas are reduced compared to those of the unexposed ones, with the exception of pentafluorophenyl methacrylate (PFMA) homopolymer film. This is attributed to the reaction of the epoxy groups creating x-links and producing hydroxyl groups and the cleavage of the pentafluorophenyl group from the ester group leading to carboxylic acid groups. Both modifications on the exposed areas are verified by FTIR spectroscopy and ToF-SIMS analysis. In addition, the biomolecules adsorption ability of the exposed area is increasing 10–15 times compared to the unexposed one for the PFMA homopolymer and the PFMA/VBGE 1:1 copolymer. Thus, the proposed polymers and patterning procedure could find application to spatially directed immobilization of biomolecules and/or cells onto a surface for both biosensing and tissue engineering purposes.

Original language	English (US)
Pages (from-to)	493
Journal	Polymers
Volume	15
Issue number	3
DOIs	https://doi.org/10.3390/polym15030493
State	Published - Jan 17 2023

Bibliographical note

KAUST Repository Item: Exported on 2023-01-23
Acknowledgements: This research is co-financed by Greece and the European Union (European Social FundESF) through the Operational Programme «Human Resources Development, Education and Lifelong Learning 2014- 2020» in the context of the project “Bio-functional surfaces of fluoropolymers via lithography techniques” (MIS: 5048147). : We acknowledge financial support for publishing this work by the Special Account for Research Grants of the National and Kapodistrian University of Athens (SARG UoA).

ASJC Scopus subject areas

General Chemistry
Polymers and Plastics

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10.3390/polym15030493

https://repository.kaust.edu.sa/bitstream/10754/687227/1/polymers-15-00493-v2.pdf

Cite this

@article{4c4b5b6b3a314eb09c3529382d517682,

title = "Post-Polymerization Modification of Fluoropolymers via UV Irradiation in the Presence of a Photoacid Generator",

abstract = "Fluorinated polymers have unique wettability and protein adsorption properties. The site-specific alteration of these properties could expand their application to different research areas. In this work, a fluorinated homopolymer and two of its copolymers with 4-vinylbenzyl glycidyl ether (VBGE) are synthesized by free radical polymerization. The produced polymers are then used to develop resist formulations by the addition of a photoacid generator. Films of these formulations are exposed to ultraviolet radiation through a binary mask and heated to create the pattern. It is found that the water contact angle values of the exposed films areas are reduced compared to those of the unexposed ones, with the exception of pentafluorophenyl methacrylate (PFMA) homopolymer film. This is attributed to the reaction of the epoxy groups creating x-links and producing hydroxyl groups and the cleavage of the pentafluorophenyl group from the ester group leading to carboxylic acid groups. Both modifications on the exposed areas are verified by FTIR spectroscopy and ToF-SIMS analysis. In addition, the biomolecules adsorption ability of the exposed area is increasing 10–15 times compared to the unexposed one for the PFMA homopolymer and the PFMA/VBGE 1:1 copolymer. Thus, the proposed polymers and patterning procedure could find application to spatially directed immobilization of biomolecules and/or cells onto a surface for both biosensing and tissue engineering purposes.",

author = "Anastasia Nika and Christina Gkioka and Fotini Machairioti and Panagiotis Bilalis and Jiaxi Xu and Katarzyna Gajos and Kamil Awsiuk and Panagiota Petrou and Margarita Chatzichristidi",

note = "KAUST Repository Item: Exported on 2023-01-23 Acknowledgements: This research is co-financed by Greece and the European Union (European Social FundESF) through the Operational Programme «Human Resources Development, Education and Lifelong Learning 2014- 2020» in the context of the project “Bio-functional surfaces of fluoropolymers via lithography techniques” (MIS: 5048147). : We acknowledge financial support for publishing this work by the Special Account for Research Grants of the National and Kapodistrian University of Athens (SARG UoA).",

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month = jan,

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doi = "10.3390/polym15030493",

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T1 - Post-Polymerization Modification of Fluoropolymers via UV Irradiation in the Presence of a Photoacid Generator

AU - Nika, Anastasia

AU - Gkioka, Christina

AU - Machairioti, Fotini

AU - Bilalis, Panagiotis

AU - Xu, Jiaxi

AU - Gajos, Katarzyna

AU - Awsiuk, Kamil

AU - Petrou, Panagiota

AU - Chatzichristidi, Margarita

N1 - KAUST Repository Item: Exported on 2023-01-23 Acknowledgements: This research is co-financed by Greece and the European Union (European Social FundESF) through the Operational Programme «Human Resources Development, Education and Lifelong Learning 2014- 2020» in the context of the project “Bio-functional surfaces of fluoropolymers via lithography techniques” (MIS: 5048147). : We acknowledge financial support for publishing this work by the Special Account for Research Grants of the National and Kapodistrian University of Athens (SARG UoA).

PY - 2023/1/17

Y1 - 2023/1/17

N2 - Fluorinated polymers have unique wettability and protein adsorption properties. The site-specific alteration of these properties could expand their application to different research areas. In this work, a fluorinated homopolymer and two of its copolymers with 4-vinylbenzyl glycidyl ether (VBGE) are synthesized by free radical polymerization. The produced polymers are then used to develop resist formulations by the addition of a photoacid generator. Films of these formulations are exposed to ultraviolet radiation through a binary mask and heated to create the pattern. It is found that the water contact angle values of the exposed films areas are reduced compared to those of the unexposed ones, with the exception of pentafluorophenyl methacrylate (PFMA) homopolymer film. This is attributed to the reaction of the epoxy groups creating x-links and producing hydroxyl groups and the cleavage of the pentafluorophenyl group from the ester group leading to carboxylic acid groups. Both modifications on the exposed areas are verified by FTIR spectroscopy and ToF-SIMS analysis. In addition, the biomolecules adsorption ability of the exposed area is increasing 10–15 times compared to the unexposed one for the PFMA homopolymer and the PFMA/VBGE 1:1 copolymer. Thus, the proposed polymers and patterning procedure could find application to spatially directed immobilization of biomolecules and/or cells onto a surface for both biosensing and tissue engineering purposes.

AB - Fluorinated polymers have unique wettability and protein adsorption properties. The site-specific alteration of these properties could expand their application to different research areas. In this work, a fluorinated homopolymer and two of its copolymers with 4-vinylbenzyl glycidyl ether (VBGE) are synthesized by free radical polymerization. The produced polymers are then used to develop resist formulations by the addition of a photoacid generator. Films of these formulations are exposed to ultraviolet radiation through a binary mask and heated to create the pattern. It is found that the water contact angle values of the exposed films areas are reduced compared to those of the unexposed ones, with the exception of pentafluorophenyl methacrylate (PFMA) homopolymer film. This is attributed to the reaction of the epoxy groups creating x-links and producing hydroxyl groups and the cleavage of the pentafluorophenyl group from the ester group leading to carboxylic acid groups. Both modifications on the exposed areas are verified by FTIR spectroscopy and ToF-SIMS analysis. In addition, the biomolecules adsorption ability of the exposed area is increasing 10–15 times compared to the unexposed one for the PFMA homopolymer and the PFMA/VBGE 1:1 copolymer. Thus, the proposed polymers and patterning procedure could find application to spatially directed immobilization of biomolecules and/or cells onto a surface for both biosensing and tissue engineering purposes.

UR - http://hdl.handle.net/10754/687227

UR - https://www.mdpi.com/2073-4360/15/3/493

U2 - 10.3390/polym15030493

DO - 10.3390/polym15030493

M3 - Article

C2 - 36771794

SN - 2073-4360

VL - 15

SP - 493

JO - Polymers

JF - Polymers

IS - 3

ER -

Post-Polymerization Modification of Fluoropolymers via UV Irradiation in the Presence of a Photoacid Generator

Abstract

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ASJC Scopus subject areas

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