Reactivity Ratios and Surface Properties of Confined and Bulk ATRP Copolymerization of Butyl Methacrylate and 2-Hydroxyethyl Acrylate

Abstract

Tunable hardness materials have shown fascinating properties, which place them as potential materials for use in different technological fields. This work deals with the bulk and confined synthesis of copolymers based on butyl methacrylate and 2-hydroxyethyl acrylate (HEA), prepared by atom transfer radical copolymerization in the entire composition range using conventional and anodic aluminum oxide (AAO) reactors, respectively. In each case, reactivity ratios and molecular weights were calculated using nuclear magnetic resonance, and the latter were compared to the values obtained by size exclusion chromatography. Differential scanning calorimetry and thermogravimetric analysis allowed to evaluate thermal transition and decomposition profiles and, with this data, compare the differences in each system, bulk and confined. Finally, the nanostructures extracted from the AAO nanoreactor were evaluated on the surface by atomic force microscopy and the water contact angle. Interestingly, our results revealed remarkable differences in the reactivity ratios under bulk and confined conditions. Nanopolymerization increased the reactivity of the HEA monomer, and the thermal and surface analysis supported this observation. Indeed, these results will bring valuable knowledge that will advance the field of application of nanopolymeric materials as well as their potential applications in surface science.

In Situ NMR Measurement of Reactivity Ratios for the Copolymerization of 3,4-Dimethoxystyrene and para-Substituted Styrene

“…The monomer reactivity ratios in a copolymerization reaction are mainly dependent on the molecular structures of the monomers. However, the reaction conditions may play a considerable role in the reactivity ratios. , The solvent’s effect on the reactivity ratios was examined for the copolymerization of 3,4-dimethoxystyrene and styrene at 70 °C in toluene- d 8 and DMSO- d 6 . The reactivity ratios determined by the Mayo–Lewis method are r styrene = 1.00 ± 0.02 and r 3,4‑DMS = 1.06 ± 0.02 in DMSO- d 6 in comparison to r styrene = 0.89 ± 0.04 and r 3,4‑DMS = 1.53 ± 0.06 in toluene- d 8 , as shown in Tables and .…”

Hierarchically Structured Nanotube Arrays as Heterogenous Photocatalysts for Highly Efficient Broadband Photoinduced Controlled Radical Polymerization

“…The unique highly ordered vertical 1D nanotube structure is conducive to accelerate the rapid transfer of electrons, which makes it possible to circumvent the constraints of relatively short charge diffusion lengths; thus, a more efficient photocatalytic polymerization reaction could be realized. 36 To further confirm the above results, the electron transfer efficiencies of the TNTAs and TiO 2 nanoparticle photocatalysts were indirectly compared by measuring the evolution of the UV−vis absorption peak intensity of the Cu(II) in the catalytic system (Figure 2c−d). 37 After irradiation for 3 h under UV light, the maximum absorption peak intensity attributed to Cu(II) in TiO 2 NPs system at the wavelength of about 700 nm decreases from 1.4 to 0.7, while that in the TNTAs system decreases from 1.4 to 0.5.…”

“…The nanotube wall of highly ordered TiO 2 nanotube arrays could provide large specific internal surface area, an oriented charge transfer channel with high light harvesting efficiency, and high electron mobility. The unique highly ordered vertical 1D nanotube structure is conducive to accelerate the rapid transfer of electrons, which makes it possible to circumvent the constraints of relatively short charge diffusion lengths; thus, a more efficient photocatalytic polymerization reaction could be realized . To further confirm the above results, the electron transfer efficiencies of the TNTAs and TiO 2 nanoparticle photocatalysts were indirectly compared by measuring the evolution of the UV–vis absorption peak intensity of the Cu­(II) in the catalytic system (Figure c–d) .…”

The unique role of pore wall nanostructurization in the intrachannel photo-ATRP for fine-tuning PMMA tacticity

“…In this context, it is noteworthy that following intrachannel polymerization protocols: photo-, 3 and thermally- 3 ,induced free-radical polymerization (FRP), photo-, 4 and thermally- 5,6 , induced reversible-addition fragmentation chain transfer polymerization (RAFT), ring-opening polymerization (ROP), 7 and polycondensation 8 have been reported in the literature so far. Remarkably, these elegant strategies utilized nano/mesoreactors in the form of silica-(SiO 2 ) 9,10,11 , aluminum oxide (AAO) 12,13,12,14 templates/plates, and metal-organic frameworks 15,6,9, /zeolites 16 powders. Many experimental studies and simulations revealed that due to the specific interactions occurring at the interface, there is higher local concentration of molecules, and reduced diffusivity of chains (in the close proximity of the pore walls).…”

“…(AAO) [12][13][14] templates/plates, and metal-organic frameworks, 6,9,15 and zeolite 16 powders. Many experimental studies and simulations revealed that due to the specific interactions occurring at the interface, there is a higher local concentration of molecules, and reduced diffusivity of chains (in close proximity to the pore walls).…”