Wood-Mimicking Bio-Based Biporous Polymeric Materials with Anisotropic Tubular Macropores

Abstract

Understanding physical phenomena related to fluid flow transport in plants and especially through wood is still a major challenge for the scientific community. To this end, we have focused our attention on the design of wood-mimicking polymeric architectures through a strategy based on the double porogen templating approach which relies on the use of two distinct types of porogens, namely aligned nylon threads and a porogenic solvent, to produce macro- and nanoporosity levels, respectively. A bio-based phenolic functional monomer, i.e., vanillin methacrylate, was employed to mimic either hard wood or soft wood. Upon free-radical polymerization with a crosslinking agent in the presence of both types of porogenic agents, followed by their removal, biporous materials with anistotropic tubular macropores surrounded by a nanoporous matrix were obtained. They were further fully characterized in terms of porosity and chemical composition via mercury intrusion porosimetry, scanning electron microscopy and X-ray microtomography. It was demonstrated that the two porosity levels could be independently tuned by varying structural parameters. Further, the possibility to chemically modify the pore surface and thus to vary the material surface properties was successfully demonstrated by reductive amination with model compounds via Raman spectroscopy and water contact angle measurements.

TG/DSC/FTIR/QMS analysis of environmentally friendly poly(citronellyl methacrylate)-co-poly(benzyl methacrylate) copolymers

“…At T max1a , the presence of the m/z ions characteristic for the emission of benzyl methacrylate monomer is observed (m/ z 39, 41, 65, 69, 79, 90, 91, 107, 131) [58]. In addition, the QMS spectra show the presence of m/z ions: 27,29,37,38,39,40,41,42,43,50,51,52,53,54,55,56,57,58,65,67,68,69,70,77,79,91, 92 which are derived from decomposition products such as citronellyl methacrylate, citronellal and 2-methylpropenal. At T max2 , mainly the emission of H 2 O (m/z 16, 17, 18), CO 2 (m/z 44) and CO (m/z 28) is visible [58] which indicate on the combustion processes of the formed residues [60,61].…”

“…The presence of the absorption signals for the carbonyl group with two maxima and the presence of the exothermic DSC peak may indicate the formation of ester and the decomposition products with lower masses. Analyzing the QMS spectra, the presence of m/z ions characteristic for citronellyl methacrylate such as 50, 51, 52, 53, 54, 55, 56, 57, 58, 65, 68, 69, 70, 77, 79, 91, 92 [38, 58] and for the decomposition products of citronellyl methacrylate such as 2-methylpropenal (m/z 41,70,39,42,29,38,40,27,37,69) and citronellal (m/z 41, 69, 55,95,43,56,67,29,39,27) is noticed, Scheme 2. However, due to the presence of an exothermic peak on the DSC, it is highly probable that the formed unsaturated aldehydes can undergo polymerization under the test conditions to form compounds with higher molecular masses.…”

“…So far, it is known to use isosorbide to obtain acetylated acrylic and methacrylic isosorbide monomers by the tandem esterification with acetic anhydride and methacrylic anhydride [19][20][21][22] or syringyl methacrylate, creosyl methacrylate [23][24][25], vanillin methacrylate [24][25][26] to prepare bio-based polymeric materials for high-temperature applications. The use of new alkyl lactate monomers (methyl, ethyl, npropyl and n-butyl lactate acrylates) to the preparation of bio-based acrylates is also known [27][28][29][30][31]. The synthesis of fatty acid-based meth(acrylate) monomers prepared in the esterification process of fatty alcohols with different chain lengths and meth(acrylic) acids or meth(acryloyl chlorides) or in the transesterification process of fatty alcohols with different chain lengths and meth(acrylates), e.g., methyl methacrylate is also described [32].…”