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Design of nanostructured hybrid materials: twin polymerization of urethane-based twin prepolymers.

ABSTRACT: Organic-inorganic hybrid materials with urethane functionalities were obtained by simultaneous twin polymerization of twin prepolymers in combination with the ideal twin monomer 2,2'-spirobi[4H-1,3,2-benzodioxasiline]. The twin prepolymers consist of a urethane-based prepolymer with reactive terminal groups which can react during the twin polymerization process. Nanostructured hybrid materials with integrated dialkylsiloxane crosslinked urethane structures, phenolic resin and SiO₂ are obtained in a one pot process. The effects of the polymerization temperature as well as those of various catalysts and reagent ratios on the polymerization behavior were investigated. The molecular structures of the obtained materials were determined by ¹³C- and ²⁹Si-{¹H}-CP-MAS NMR spectroscopies. HAADF-STEM-measurements were performed to prove the distribution of silicon in the hybrid material.

SUBMITTER: Uhlig D

PROVIDER: S-EPMC9085902 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature

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Design of nanostructured hybrid materials: twin polymerization of urethane-based twin prepolymers.

Uhlig D D Spange S S Seifert A A Nagel K K Anders S S Kroll L L Stoll R R Thielbeer F F Müller P P Schreiter K K

RSC advances 20180912 55

Organic-inorganic hybrid materials with urethane functionalities were obtained by simultaneous twin polymerization of twin prepolymers in combination with the ideal twin monomer 2,2'-spirobi[4<i>H</i>-1,3,2-benzodioxasiline]. The twin prepolymers consist of a urethane-based prepolymer with reactive terminal groups which can react during the twin polymerization process. Nanostructured hybrid materials with integrated dialkylsiloxane crosslinked urethane structures, phenolic resin and SiO<sub>2</s ...[more]

PMID: 35548201

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Project description:The purpose of this work was to investigate the effect of multifunctionality on material properties of synthetic polymer aerogels. For this purpose, we present the synthesis and characterization of monolithic dendritic-type urethane-acrylate monomers based on an aliphatic/flexible (Desmodur N3300), or an aromatic/rigid (Desmodur RE) triisocyanate core. The terminal acrylate groups (three at the tip of each of the three branches, nine in total) were polymerized with 2,2'-azobis(isobutyronitrile) (AIBN) via free radical chemistry. The resulting wet-gels were dried with supercritical fluid (SCF) CO₂. Aerogels were characterized with ATR-FTIR and solid-state 13C NMR. The porous network was probed with N₂-sorption and scanning electron microscopy (SEM). The thermal stability of aerogels was studied with thermogravimetric analysis (TGA). Most aerogels were macroporous materials (porosity > 80%), with high thermal stability (up to 300 °C). Aerogels were softer at low monomer concentrations and more rigid at higher concentrations. The material properties were compared with those of analogous aerogels bearing only one acrylate moiety at the tip of each branch and the same cores, and with those of analogous aerogels bearing norbornene instead of acrylate moieties. The nine-terminal acrylate-based monomers of this study caused rapid decrease of the solubility of the growing polymer and made possible aerogels with much smaller particles and much higher surface areas. For the first time, aliphatic/flexible triisocyanate-based materials could be made with similar properties in terms of particle size and surface areas to their aromatic/rigid analogues. Finally, it was found that with monomers with a high number of crosslinkable groups, material properties are determined by multifunctionality and thus aerogels based on 9-acrylate- and 9-norbornene-terminated monomers were similar. Materials with aromatic cores are carbonizable with satisfactory yields (20⁻30% w/w) to mostly microporous materials (BET surface areas: 640⁻740 m² g-1; micropore surface areas: 360⁻430 m² g-1).

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Design of nanostructured hybrid materials: twin polymerization of urethane-based twin prepolymers.

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Design of nanostructured hybrid materials: twin polymerization of urethane-based twin prepolymers.

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