Surface initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA-ATRP) of 4-vinylpyridine on poly(ethylene terephthalate)

Mohamad Maaz; Tamara Elzein; Alice Bejjani; Nadine Barroca-Aubry; Bénédicte Lepoittevin; Diana Dragoe; Sandra Mazerat; Bilal Nsouli; Philippe Roger

doi:10.1016/j.jcis.2017.03.115

Surface initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA-ATRP) of 4-vinylpyridine on poly(ethylene terephthalate)

J Colloid Interface Sci. 2017 Aug 15:500:69-78. doi: 10.1016/j.jcis.2017.03.115. Epub 2017 Apr 2.

Authors

Mohamad Maaz¹, Tamara Elzein², Alice Bejjani³, Nadine Barroca-Aubry⁴, Bénédicte Lepoittevin⁴, Diana Dragoe⁴, Sandra Mazerat⁴, Bilal Nsouli³, Philippe Roger⁵

Affiliations

¹ Lebanese Atomic Energy Commission, National Council for Scientific Research, CNRS-L, Beirut, Lebanon; Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Univ Paris Sud, Université Paris Saclay, 91405, Orsay, France.
² Lebanese Atomic Energy Commission, National Council for Scientific Research, CNRS-L, Beirut, Lebanon. Electronic address: tamara.elzein@cnrs.edu.lb.
³ Lebanese Atomic Energy Commission, National Council for Scientific Research, CNRS-L, Beirut, Lebanon.
⁴ Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Univ Paris Sud, Université Paris Saclay, 91405, Orsay, France.
⁵ Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Univ Paris Sud, Université Paris Saclay, 91405, Orsay, France. Electronic address: philippe.roger@u-psud.fr.

PMID: 28399464
DOI: 10.1016/j.jcis.2017.03.115

Abstract

Poly(ethylene terephthalate) (PET) substrates were modified by means of surface-initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA-ATRP) of 4-vinylpyridine (4VP). Substrates were pretreated in order to graft chloromethylbenzene (CMB) units capable of initiating the radical polymerization reaction of 4VP units. Surface characterization techniques, including Water Contact Angle (WCA), Attenuated Total Reflection (ATR), X-ray photoelectron spectroscopy (XPS), Atomic Force Microscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) showed a successful grafting of a stable, smooth and homogenous layer of p4VP. This process offers the advantages of a rapid, simplified and low cost strategy to chemically modify polymer substrates with covalently bonded layer of the pH responsive p4VP for different applications. Moreover, by using TOF-SIMS profiling, we were able to track a density gradient along the z-axis generated by the interpenetrating phases of the different layers of the final modified surface. Fact that we correlated to the various positions of initiation sites within the polyethylenimine (PEI) used for PET aminolysis prior to CMB grafting. Our strategy will be used in future work to graft other polymers for different applications where industrial scale viable options are needed.

Keywords: 4-Vinylpyridine 4VP; Poly(ethylene terephthalate) PET; Surface-initiated supplemental activator and reducing agent atom transfer radical polymerization SARA ATRP; ToF-SIMS; XPS.