SYNTHESIS of P(N-ISOPROPYL ACRYLAMIDE - HYDROXYPROPYL METHACRYLATE) THERMO RESPONSIVE COPOLYMER FILMs BY INITIATED CHEMICAL VAPOR DEPOSITION METHOD

Year 2024, Volume: 12 Issue: 3, 687 - 699, 01.09.2024

Emine Sevgili Mercan , Kurtuluş Yılmaz , Mustafa Karaman

https://doi.org/10.36306/konjes.1408922

Abstract

This study illustrates the deposition of thermo responsive p(N-isopropyl acrylamide-hydroxypropyl methacrylate) p(NIPAAm-HPMA) copolymer thin films by initiated chemical vapor deposition (iCVD) method using tert-butyl peroxide (TBPO) as the initiator. Copolymers were deposited at three different HPMA flow rates and the effects of NIPAAm/HPMA flow rate ratio on the deposition rate, structure and responsive properties of the as-deposited films were investigated. The highest deposition rate of 50 nm/min was observed for the copolymer deposited using lowest NIPAAm/HPMA monomer ratio studied. The deposition rate showed a significant increase with decreasing NIPAAm/HPMA flow ratio. Results of FTIR and XPS spectroscopy analyses revealed a significant preservation of structural retention in iCVD p(NIPAAm-HPMA) thermo-responsive films. Lower critical solution temperatures (LCST) of p(NIPAAm-HPMA) films were determined by carrying out a temperature-dependent contact angle analysis. Accordingly, it was shown that LCST was varied between 19 and 23 oC, which was observed to be dependent on the NIPAAm/HPMA monomer ratio. That LCST range is considerably below the literature- reported values for pNIPAAM, which makes the as-deposited copolymer suitable for applications that require thermos-responsive properties at lower temperatures.

Keywords

Thermo-responsive, iCVD, LCST, Polymeric Thin Film, Hydrogel

Ethical Statement

The authors declare that all ethical guidelines including authorship, citation, data reporting, and publishing original research are followed.

Supporting Institution

Scientific Research Projects of Konya Technical University

Project Number

18201085

Thanks

This project was supported by the Scientific Research Projects of Konya Technical University with a grant number of 18201085.

References

• D. Crespy and R. M. Rossi, "Temperature‐responsive polymers with LCST in the physiological range and their applications in textiles," Polymer International, vol. 56, no. 12, pp. 1461-1468, 2007.
• S. Dai, P. Ravi, and K. C. Tam, "pH-Responsive polymers: synthesis, properties and applications," Soft Matter, vol. 4, no. 3, pp. 435-449, 2008.
• Y. Li et al., "Magnetic hydrogels and their potential biomedical applications," Advanced Functional Materials, vol. 23, no. 6, pp. 660-672, 2013.
• J. S. Katz and J. A. Burdick, "Light-Responsive Biomaterials: Development and Applications," Macromolecular Bioscience, vol. 10, no. 4, pp. 339-348, 2010, doi: https://doi.org/10.1002/mabi.200900297.
• R. V. Ulijn, "Enzyme-responsive materials: a new class of smart biomaterials," Journal of Materials Chemistry, vol. 16, no. 23, pp. 2217-2225, 2006.
• M. A. Ward and T. K. Georgiou, "Thermoresponsive polymers for biomedical applications," Polymers, vol. 3, no. 3, pp. 1215-1242, 2011.
• P. T. Mather, X. Luo, and I. A. Rousseau, "Shape memory polymer research," Annual Review of Materials Research, vol. 39, pp. 445-471, 2009.
• I. Tokarev and S. Minko, "Stimuli-responsive hydrogel thin films," Soft Matter, Review vol. 5, no. 3, pp. 511-524, 2009, doi: 10.1039/b813827c.
• M. E. Alf, T. A. Hatton, and K. K. Gleason, "Novel N-isopropylacrylamide based polymer architecture for faster LCST transition kinetics," Polymer, vol. 52, no. 20, pp. 4429-4434, 2011/09/12/ 2011, doi: https://doi.org/10.1016/j.polymer.2011.07.051.
• H. H. Nguyen, B. Payre, J. Fitremann, N. Lauth-de Viguerie, and J.-D. Marty, "Thermoresponsive properties of PNIPAM-based hydrogels: effect of molecular architecture and embedded gold nanoparticles," Langmuir, vol. 31, no. 16, pp. 4761-4768, 2015.
• W. Wei et al., "A novel thermo-responsive hydrogel based on salecan and poly (N-isopropylacrylamide): Synthesis and characterization," Colloids and Surfaces B: Biointerfaces, vol. 125, pp. 1-11, 2015.
• M. Heskins and J. E. Guillet, "Solution properties of poly (N-isopropylacrylamide)," Journal of Macromolecular Science—Chemistry, vol. 2, no. 8, pp. 1441-1455, 1968.
• A. Pena-Francesch, L. Montero, and S. Borrós, "Tailoring the LCST of thermosensitive hydrogel thin films deposited by iCVD," Langmuir, vol. 30, no. 24, pp. 7162-7167, 2014.
• K. Jain, R. Vedarajan, M. Watanabe, M. Ishikiriyama, and N. Matsumi, "Tunable LCST behavior of poly (N-isopropylacrylamide/ionic liquid) copolymers," Polymer Chemistry, vol. 6, no. 38, pp. 6819-6825, 2015.
• W. Wang et al., "Thin films of poly (N-isopropylacrylamide) end-capped with n-butyltrithiocarbonate," Macromolecules, vol. 41, no. 9, pp. 3209-3218, 2008.
• Y. Guan and Y. Zhang, "PNIPAM microgels for biomedical applications: from dispersed particles to 3D assemblies," Soft Matter, vol. 7, no. 14, pp. 6375-6384, 2011.
• M. R. Islam, A. Ahiabu, X. Li, and M. J. Serpe, "Poly (N-isopropylacrylamide) microgel-based optical devices for sensing and biosensing," Sensors, vol. 14, no. 5, pp. 8984-8995, 2014.
• X. Xu et al., "Poly (N-isopropylacrylamide)-based thermoresponsive composite hydrogels for biomedical applications," Polymers, vol. 12, no. 3, p. 580, 2020.
• J. Liu, L. Jiang, S. He, J. Zhang, and W. Shao, "Recent progress in PNIPAM-based multi-responsive actuators: A mini-review," Chemical Engineering Journal, vol. 433, p. 133496, 2022.
• Z. Ayar, M. Shafieian, N. Mahmoodi, O. Sabzevari, and Z. Hassannejad, "A rechargeable drug delivery system based on pNIPAM hydrogel for the local release of curcumin," Journal of Applied Polymer Science, vol. 138, no. 40, p. 51167, 2021.
• M. Cao et al., "Reversible thermoresponsive peptide–PNIPAM hydrogels for controlled drug delivery," Biomacromolecules, vol. 20, no. 9, pp. 3601-3610, 2019.
• X. Lu, L. Zhang, L. Meng, and Y. Liu, "Synthesis of poly (N-isopropylacrylamide) by ATRP using a fluorescein-based initiator," Polymer Bulletin, vol. 59, no. 2, pp. 195-206, 2007.
• M. Gürsoy, "Fabrication of Poly (N-isopropylacrylamide) with Higher Deposition Rate and Easier Phase Transition by Initiated Plasma Enhanced Chemical Vapor Deposition," Plasma Chemistry and Plasma Processing, pp. 1-17, 2020.
• G. Conzatti, S. Cavalie, C. Combes, J. Torrisani, N. Carrère, and A. Tourrette, "PNIPAM grafted surfaces through ATRP and RAFT polymerization: Chemistry and bioadhesion," Colloids and Surfaces B: Biointerfaces, vol. 151, pp. 143-155, 2017.
• S. J. McInnes et al., "Fabrication and characterization of a porous silicon drug delivery system with an initiated chemical vapor deposition temperature-responsive coating," Langmuir, vol. 32, no. 1, pp. 301-308, 2016.
• C. Wang et al., "Reversible ion-conducting switch by azobenzene molecule with light-controlled sol–gel transitions of the PNIPAm ion gel," ACS Applied Materials & Interfaces, vol. 12, no. 37, pp. 42202-42209, 2020.
• J. E. Wong, A. K. Gaharwar, D. Müller-Schulte, D. Bahadur, and W. Richtering, "Dual-stimuli responsive PNiPAM microgel achieved via layer-by-layer assembly: Magnetic and thermoresponsive," Journal of colloid and interface science, vol. 324, no. 1-2, pp. 47-54, 2008.
• B. Şimşek and M. Karaman, "Initiated chemical vapor deposition of poly (hexafluorobutyl acrylate) thin films for superhydrophobic surface modification of nanostructured textile surfaces," Journal of Coatings Technology and Research, vol. 17, no. 2, pp. 381-391, 2020.
• G. Ozaydin-Ince, A. M. Coclite, and K. K. Gleason, "CVD of polymeric thin films: applications in sensors, biotechnology, microelectronics/organic electronics, microfluidics, MEMS, composites and membranes," Reports on Progress in Physics, vol. 75, no. 1, p. 016501, 2011.
• K. K. Gleason, CVD Polymers: Fabrication of Organic Surfaces and Devices (CVD Polymers: Fabrication of Organic Surfaces and Devices). 2015, pp. 1-461.
• R. Sreenivasan and K. K. Gleason, "Overview of strategies for the CVD of organic films and functional polymer layers," Chemical Vapor Deposition, vol. 15, no. 4‐6, pp. 77-90, 2009.
• E. Çıtak, B. İstanbullu, H. Şakalak, M. Gürsoy, and M. Karaman, "All‐Dry Hydrophobic Functionalization of Paper Surfaces for Efficient Transfer of CVD Graphene," Macromolecular Chemistry and Physics, vol. 220, no. 22, p. 1900277, 2019.
• F. Z. Pour, H. Karimi, and V. M. Avargani, "Preparation of a superhydrophobic and superoleophilic polyester textile by chemical vapor deposition of dichlorodimethylsilane for Water–Oil separation," Polyhedron, vol. 159, pp. 54-63, 2019.
• H. Şakalak, K. Yılmaz, M. Gürsoy, and M. Karaman, "Roll-to roll initiated chemical vapor deposition of super hydrophobic thin films on large-scale flexible substrates," Chemical Engineering Science, vol. 215, 2020, doi: 10.1016/j.ces.2019.115466.
• K. Yılmaz, H. s. Şakalak, M. Gürsoy, and M. Karaman, "Initiated Chemical Vapor Deposition of Poly (Ethylhexyl Acrylate) Films in a Large-Scale Batch Reactor," Industrial & Engineering Chemistry Research, vol. 58, no. 32, pp. 14795-14801, 2019.
• M. Gürsoy and M. Karaman, "Hydrophobic coating of expanded perlite particles by plasma polymerization," Chemical Engineering Journal, vol. 284, pp. 343-350, 2016.
• M. N. Subramaniam, P. S. Goh, E. Sevgili, M. Karaman, W. J. Lau, and A. F. Ismail, "Hydroxypropyl methacrylate thin film coating on polyvinylidene fluoride hollow fiber membranes via initiated chemical vapor deposition," European Polymer Journal, vol. 122, 2020, doi: 10.1016/j.eurpolymj.2019.109360.
• M. Karaman and N. Çabuk, "Initiated chemical vapor deposition of pH responsive poly (2-diisopropylamino) ethyl methacrylate thin films," Thin Solid Films, vol. 520, no. 21, pp. 6484-6488, 2012.
• E. Çıtak et al., "Vapor deposition of quaternary ammonium methacrylate polymers with high antimicrobial activity: Synthetic route, toxicity assessment, and durability analysis," Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, vol. 38, no. 4, p. 043203, 2020.
• M. E. Alf, "Functional and responsive surfaces via initiated chemical vapor deposition (iCVD)," Massachusetts Institute of Technology, 2011.
• E. Sevgili and M. Karaman, "Initiated chemical vapor deposition of poly (Hydroxypropyl methacrylate) thin films," Thin Solid Films, vol. 687, p. 137446, 2019.
• M. Kurečič, M. Sfiligoj-Smole, and K. Stana-Kleinschek, "UV polymerization of poly (N-isopropylacrylamide) hydrogel," Materiali in tehnologije, vol. 46, no. 1, pp. 87-91, 2012.
• G. Beamson and D. Briggs, "High resolution monochromated X-ray photoelectron spectroscopy of organic polymers: a comparison between solid state data for organic polymers and gas phase data for small molecules," Molecular Physics, vol. 76, no. 4, pp. 919-936, 1992.
• J.-F. Lutz, Ö. Akdemir, and A. Hoth, "Point by point comparison of two thermosensitive polymers exhibiting a similar LCST: is the age of poly (NIPAM) over?," Journal of the American Chemical Society, vol. 128, no. 40, pp. 13046-13047, 2006.
• H. G. Schild, "Poly(N-isopropylacrylamide): experiment, theory and application," Progress in Polymer Science, vol. 17, no. 2, pp. 163-249, 1992/01/01/ 1992, doi: https://doi.org/10.1016/0079-6700(92)90023-R.
• E. S. Gil and S. M. Hudson, "Stimuli-reponsive polymers and their bioconjugates," Progress in Polymer Science, vol. 29, no. 12, pp. 1173-1222, 2004/12/01/ 2004, doi: https://doi.org/10.1016/j.progpolymsci.2004.08.003.
• T. Sun et al., "Reversible switching between superhydrophilicity and superhydrophobicity," Angewandte Chemie International Edition, vol. 43, no. 3, pp. 357-360, 2004.