Effect of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes on Structure-Property Relationships of Thermostable Hybrid Cyanate Ester Resin Based Nanocomposites

Olga Grigoryeva; Alexander Fainleib; Olga Starostenko; Diana Shulzhenko; Agustin Rios de Anda; Fabrice Gouanve; Eliane Espuche; Daniel Grande

doi:10.3390/polym15244654

Effect of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes on Structure-Property Relationships of Thermostable Hybrid Cyanate Ester Resin Based Nanocomposites

Polymers (Basel). 2023 Dec 9;15(24):4654. doi: 10.3390/polym15244654.

Authors

Olga Grigoryeva¹, Alexander Fainleib¹, Olga Starostenko¹, Diana Shulzhenko¹, Agustin Rios de Anda², Fabrice Gouanve³, Eliane Espuche³, Daniel Grande²

Affiliations

¹ Institute of Macromolecular Chemistry, National Academy of Sciences of Ukraine, 48, Kharkivske Shose, 02155 Kyiv, Ukraine.
² Université Paris Est Creteil, CNRS, Institut de Chimie et des Matériaux Paris-Est, UMR 7182, 2 rue Henri Dunant, 94320 Thiais, France.
³ Université Claude Bernard Lyon 1, CNRS, Ingénierie des Matériaux Polymères, UMR 5223, 15 Boulevard André Latarjet, 69622 Villeurbanne, France.

Abstract

Nanocomposites of cyanate ester resin (CER) filled with three different reactive amino-functionalized polyhedral oligomeric silsesquioxane (POSS) were synthesized and characterized. The addition of a small quantity (0.1 wt.%) of amino-POSS chemically grafted to the CER network led to the increasing thermal stability of the CER matrix by 12-15 °C, depending on the type of amino-POSS. A significant increase of the glass transition temperature, T_g (DSC data), and the temperature of α relaxation, T_α (DMTA data), by 45-55 °C of the CER matrix with loading of nanofillers was evidenced. CER/POSS films exhibited a higher storage modulus than that of neat CER in the temperature range investigated. It was evidenced that CER/aminopropylisobutyl (APIB)-POSS, CER/N-phenylaminopropyl (NPAP)-POSS, and CER/aminoethyl aminopropylisobutyl (AEAPIB)-POSS nanocomposites induced a more homogenous α relaxation phenomenon with higher T_α values and an enhanced nanocomposite elastic behavior. The value of the storage modulus, E', at 25 °C increased from 2.72 GPa for the pure CER matrix to 2.99-3.24 GPa for the nanocomposites with amino-functionalized POSS nanoparticles. Furthermore, CER/amino-POSS nanocomposites possessed a higher specific surface area, gas permeability (CO₂, He), and diffusion coefficients (CO₂) values than those for neat CER, due to an increasing free volume of the nanocomposites studied that is very important for their gas transport properties. Permeability grew by about 2 (He) and 3.5-4 times (CO₂), respectively, and the diffusion coefficient of CO₂ increased approximately twice for CER/amino-POSS nanocomposites in comparison with the neat CER network. The efficiency of amino-functionalized POSS in improving the thermal and transport properties of the CER/amino-POSS nanocomposites increased in a raw of reactive POSS containing one primary (APIB-POSS) < eight secondary (NPAP-POSS) < one secondary and one primary (AEAPIB-POSS) amino groups. APIB-POSS had the least strongly pronounced effect, since it could form covalent bonds with the CER network only by a reaction of one -NH₂ group, while AEAPIB-POSS displayed the most highly marked effect, since it could easily be incorporated into the CER network via a reaction of -NH₂ and -NH- groups with -O-C≡N groups from CER.

Keywords: amino-POSS; cyanate ester resin; gas permeability; glass transition temperature; polycyanurate; thermal stability.

Grants and funding

This research received no external funding.