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Erschienen in: Journal of Sol-Gel Science and Technology 3/2019

29.06.2019 | Original Paper: Nano-structured materials (particles, fibers, colloids, composites, etc.)

Stability and degradation of PEO20PPO70PEO20 triblock copolymers in mesostructured silica

verfasst von: Brindusa Dragoi, Guillaume Laurent, Sandra Casale, Taissire Benamor, Bénédicte Lebeau, Cédric Boissière, François Ribot, Mohamed Selmane, Patrick Schmidt, David Kreher, Anne Davidson

Erschienen in: Journal of Sol-Gel Science and Technology | Ausgabe 3/2019

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Abstract

Organic−inorganic hybrid mesostructured silicas are prepared, without stirring (at pH = 0.0) and with stirring (at pH = 0.6) to obtain isolated and gyroidal-like attached silica grains with incorporated triblock P123 poly (ethylene oxide)-poly (propylene oxide)–poly (ethylene oxide) copolymers. Selected hybrids are submitted to various thermal and aging treatments for studying hydrolysis and oxidation of PEO and PPO chains. Two complementary spectroscopic techniques are used: near-infrared (NIR) with measurements performed in diffuse reflectance, as well as 1H and 13C liquid- and solid-state nuclear magnetic resonance (NMR) to study the mobility and stability of PEO and PPO chains. With precipitated fresh hybrids, the ratio of PEO over (PEO + PPO) units is lower (30% ± 5%) than in theory. This ratio also decreases depending on temperature when a hydrothermal treatment is applied. An acidic hydrolysis involving both PEO and PPO chains, with generated fragments eliminated by washing with water and/or synthesis liquor, is then demonstrated. For comparison, another hybrid obtained by spray drying via evaporation-induced self assembly mechanism is also studied. Its NMR signals are much more stable than those of the samples prepared by precipitation. Depending on aging time, thermal history, and materials processing, the textural properties and template decomposition inside mesostructured silica are found significantly different. The influence of the hydrolysis and oxidation of the template onto final materials texture is likely to be as important as the processing conditions.

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Literatur
1.
Zurück zum Zitat Kerkhofs S, Saidi F, Vandervoort N, Van den Mooter G, Martineau C, Taulelle F, Martens J (2015) Silica capsules enclosing P123 triblock copolymer micelles for flurbiprofen storage and release. J Mat Chem B 3:3054–3061CrossRef Kerkhofs S, Saidi F, Vandervoort N, Van den Mooter G, Martineau C, Taulelle F, Martens J (2015) Silica capsules enclosing P123 triblock copolymer micelles for flurbiprofen storage and release. J Mat Chem B 3:3054–3061CrossRef
2.
Zurück zum Zitat Taguchi A, Schüth F (2005) Ordered mesoporous materials in catalysis. Microp Mesop Mat 77:1–45CrossRef Taguchi A, Schüth F (2005) Ordered mesoporous materials in catalysis. Microp Mesop Mat 77:1–45CrossRef
3.
Zurück zum Zitat Zhao D, Feng J, Huo Q, Melosh N, Fredrickson GH, Chmelka BF, Stucky GD (1998) Triblock copolymer synthesis of mesoporous silica with periodic 50 to 300 Å pores Science 279(5350):548–552CrossRef Zhao D, Feng J, Huo Q, Melosh N, Fredrickson GH, Chmelka BF, Stucky GD (1998) Triblock copolymer synthesis of mesoporous silica with periodic 50 to 300 Å pores Science 279(5350):548–552CrossRef
4.
Zurück zum Zitat Ruthstein S, Schmidt J, Kesselman E, Talmon Y, Goldfarb D (2006) Resolving intermediate solution structures during the formation of mesoporous SBA-15. J Am Chem Soc. 128:3366–3374CrossRef Ruthstein S, Schmidt J, Kesselman E, Talmon Y, Goldfarb D (2006) Resolving intermediate solution structures during the formation of mesoporous SBA-15. J Am Chem Soc. 128:3366–3374CrossRef
5.
Zurück zum Zitat Khodakov A, Zholobenko VL, Impéror-Clerc M, Durand D (2005) Characterization of the initial stages of SBA-15 synthesis by in situ time-resolved small-angle X-ray scattering. J Phys Chem B 109(48):22780–22790CrossRef Khodakov A, Zholobenko VL, Impéror-Clerc M, Durand D (2005) Characterization of the initial stages of SBA-15 synthesis by in situ time-resolved small-angle X-ray scattering. J Phys Chem B 109(48):22780–22790CrossRef
6.
Zurück zum Zitat Firouzi A, Atef F, Oertli AG, Stucky GD, Chmelka BF (1997) Alkaline lyotropic silicate−surfactant liquid crystals. J Am Chem Soc 119(15):3596–3610CrossRef Firouzi A, Atef F, Oertli AG, Stucky GD, Chmelka BF (1997) Alkaline lyotropic silicate−surfactant liquid crystals. J Am Chem Soc 119(15):3596–3610CrossRef
7.
Zurück zum Zitat Yang CM, Zibrowius B, Schmidt W, Schüth F (2004) Stepwise removal of the copolymer template from mesopores and micropores in SBA-15. Chem Mater 16(15):2918–2925CrossRef Yang CM, Zibrowius B, Schmidt W, Schüth F (2004) Stepwise removal of the copolymer template from mesopores and micropores in SBA-15. Chem Mater 16(15):2918–2925CrossRef
8.
Zurück zum Zitat Bae YK, Han OH (2008) Solid-state NMR study on the structure and dynamics of triblock copolymer P123 remaining in SBA-15 after solvent washing. Bull Korean Chem Soc 29(5):911–912CrossRef Bae YK, Han OH (2008) Solid-state NMR study on the structure and dynamics of triblock copolymer P123 remaining in SBA-15 after solvent washing. Bull Korean Chem Soc 29(5):911–912CrossRef
9.
Zurück zum Zitat Zhang Z, Yin J, Heeres HJ, Melián-Cabrera I (2013) Thermal detemplation of SBA-15 mesophases. Effect of the activation protocol on the framework contraction Microp Mesop Mat 176:103–111CrossRef Zhang Z, Yin J, Heeres HJ, Melián-Cabrera I (2013) Thermal detemplation of SBA-15 mesophases. Effect of the activation protocol on the framework contraction Microp Mesop Mat 176:103–111CrossRef
10.
Zurück zum Zitat Manet S, Schmitt J, Impéror-Clerc M, Zholobenko V, Durand D, Oliveira CLP, Pedersen JS, Gervais C, Baccile N, Babonneau F, Grillo I, Meneau F, Rochas C (2011) Kinetics of the formation of 2D-hexagonal silica nanostructured materials by nonionic block copolymer templating in solution. J Phys Chem B 115(39):11330–11344CrossRef Manet S, Schmitt J, Impéror-Clerc M, Zholobenko V, Durand D, Oliveira CLP, Pedersen JS, Gervais C, Baccile N, Babonneau F, Grillo I, Meneau F, Rochas C (2011) Kinetics of the formation of 2D-hexagonal silica nanostructured materials by nonionic block copolymer templating in solution. J Phys Chem B 115(39):11330–11344CrossRef
11.
Zurück zum Zitat Manet S, Lecchi A, Impéror-Clerc M, Zholobenko V, Durand D, Oliveira CLP, Pedersen JS, Grillo I, Meneau F, Rochas C (2011) Structure of micelles of a nonionic block copolymer determined by SANS and SAXS. J Phys Chem B115(39):11318–11329CrossRef Manet S, Lecchi A, Impéror-Clerc M, Zholobenko V, Durand D, Oliveira CLP, Pedersen JS, Grillo I, Meneau F, Rochas C (2011) Structure of micelles of a nonionic block copolymer determined by SANS and SAXS. J Phys Chem B115(39):11318–11329CrossRef
12.
Zurück zum Zitat Sayari A, Han BH, Yang Y (2004) Simple synthesis route to monodispersed SBA-15 Silica Rods. J Am Chem Soc 126(44):14348–14349CrossRef Sayari A, Han BH, Yang Y (2004) Simple synthesis route to monodispersed SBA-15 Silica Rods. J Am Chem Soc 126(44):14348–14349CrossRef
13.
Zurück zum Zitat Yu K, Smarsly B, Brinker CJ (2003) Self-assembly and characterization of mesostructured silica films with a 3D arrangement of isolated spherical mesopores. Adv Funct Mater 13(1):47–52CrossRef Yu K, Smarsly B, Brinker CJ (2003) Self-assembly and characterization of mesostructured silica films with a 3D arrangement of isolated spherical mesopores. Adv Funct Mater 13(1):47–52CrossRef
14.
Zurück zum Zitat Boissière C, Grosso D, Amenitsch H, Gibaud A, Coupé A, Baccile N, Sanchez C (2003) First in-situ SAXS studies of the mesostructuration of spherical silica and titania particles during spray-drying process. Chem Commun 21:2798–2799CrossRef Boissière C, Grosso D, Amenitsch H, Gibaud A, Coupé A, Baccile N, Sanchez C (2003) First in-situ SAXS studies of the mesostructuration of spherical silica and titania particles during spray-drying process. Chem Commun 21:2798–2799CrossRef
15.
Zurück zum Zitat Boissiere C, Grosso D, Chamonnot A, Nicole L, Sanchez C (2011) Aerosol route to functional nanostructured inorganic and hybrids porous materials. Adv Mater 23:599–623CrossRef Boissiere C, Grosso D, Chamonnot A, Nicole L, Sanchez C (2011) Aerosol route to functional nanostructured inorganic and hybrids porous materials. Adv Mater 23:599–623CrossRef
16.
Zurück zum Zitat Yu GE, Altinok H, Nixon SK, Booth C, Alexandridis P, Halton TA (1997) Self –association properties of oxyethylene/oxypropylene/oxyethylene triblock copolymers F88. Eur. Polym. 33(5):673–677CrossRef Yu GE, Altinok H, Nixon SK, Booth C, Alexandridis P, Halton TA (1997) Self –association properties of oxyethylene/oxypropylene/oxyethylene triblock copolymers F88. Eur. Polym. 33(5):673–677CrossRef
17.
Zurück zum Zitat Christy AA (2010) New insights into the surface functionalities and adsorption evolution of water molecules on silica gel surface: a study by second derivative near infrared spectroscopy. Vib Spectrosc 54(1):42–49CrossRef Christy AA (2010) New insights into the surface functionalities and adsorption evolution of water molecules on silica gel surface: a study by second derivative near infrared spectroscopy. Vib Spectrosc 54(1):42–49CrossRef
18.
Zurück zum Zitat Workman JJ (1996) Interpretative spectroscopy for near infrared. Appl Spectrosc Rev 31(3):251–320CrossRef Workman JJ (1996) Interpretative spectroscopy for near infrared. Appl Spectrosc Rev 31(3):251–320CrossRef
19.
Zurück zum Zitat GenkawaT WatariM, NishiiT, Suzuki M, Ozaki Y (2013) Two-dimensional heterospectral correlation analysis of water and liquid oleic acid using an online near-infrared/mid-infrared dual-region spectrometer. Appl Spectrosc 67(7):724–730CrossRef GenkawaT WatariM, NishiiT, Suzuki M, Ozaki Y (2013) Two-dimensional heterospectral correlation analysis of water and liquid oleic acid using an online near-infrared/mid-infrared dual-region spectrometer. Appl Spectrosc 67(7):724–730CrossRef
20.
Zurück zum Zitat Hourant P, Baeten V, Morales MT, Meurens M, Aparicio R (2000) Oil and fat classification by selected bands of near-infrared spectroscopy. Appl. Spectrosc 54(8):1168–1174CrossRef Hourant P, Baeten V, Morales MT, Meurens M, Aparicio R (2000) Oil and fat classification by selected bands of near-infrared spectroscopy. Appl. Spectrosc 54(8):1168–1174CrossRef
21.
Zurück zum Zitat Omar AF, Atan H, MatJafri MZ (2012) NIR spectroscopic properties of aqueous acids solutions. Molecules 17(6):7440CrossRef Omar AF, Atan H, MatJafri MZ (2012) NIR spectroscopic properties of aqueous acids solutions. Molecules 17(6):7440CrossRef
22.
Zurück zum Zitat Schmidt P, Badou A, Fröhlich F (2011) Detailed FT near-infrared study of the behaviour of water and hydroxyl in sedimentary length-fast chalcedony, SiO2 upon heat treatment. SpectroChimActaA 81(1):552–559CrossRef Schmidt P, Badou A, Fröhlich F (2011) Detailed FT near-infrared study of the behaviour of water and hydroxyl in sedimentary length-fast chalcedony, SiO2 upon heat treatment. SpectroChimActaA 81(1):552–559CrossRef
23.
Zurück zum Zitat Schmidt P, Masses LG, Slodczyk A, Le Bourhis E, Perrenoud C, Livage J, Fröhlich F (2012) Crystallographic and structural transformations of sedimentary chalcedony in flint upon heat treatment. J. Archeol. Sci. 39(1):135–144CrossRef Schmidt P, Masses LG, Slodczyk A, Le Bourhis E, Perrenoud C, Livage J, Fröhlich F (2012) Crystallographic and structural transformations of sedimentary chalcedony in flint upon heat treatment. J. Archeol. Sci. 39(1):135–144CrossRef
24.
Zurück zum Zitat Schmidt P, Lauer C, Buck G, Miller CE, Nickel KG (2017) Detailed near-infrared study of the ‘water’-related transformations in silica upon heat treatment. Phys Chem Miner 44(1):21–31CrossRef Schmidt P, Lauer C, Buck G, Miller CE, Nickel KG (2017) Detailed near-infrared study of the ‘water’-related transformations in silica upon heat treatment. Phys Chem Miner 44(1):21–31CrossRef
25.
Zurück zum Zitat Langer K, FlörkeOW (1974) Near infrared absorption spectra (4000–9000 cm-1) of opals and the role “water” in these SiO2·nH2O minerals. Fortschritte Mineral 52:17–51 Langer K, FlörkeOW (1974) Near infrared absorption spectra (4000–9000 cm-1) of opals and the role “water” in these SiO2·nH2O minerals. Fortschritte Mineral 52:17–51
26.
Zurück zum Zitat Fulmer GR, Miller AJM, Sherden NH, Gottlieb HE, Nudelman E, Stoltz BM, Bercaw JE, Goldberg KI (2010) NMR chemical shifts of trace impurities: common laboratory solvents, organics, and gases in deuterated solvents relevant to the organometallic chemist. Organometallics 29(9):2176–2179CrossRef Fulmer GR, Miller AJM, Sherden NH, Gottlieb HE, Nudelman E, Stoltz BM, Bercaw JE, Goldberg KI (2010) NMR chemical shifts of trace impurities: common laboratory solvents, organics, and gases in deuterated solvents relevant to the organometallic chemist. Organometallics 29(9):2176–2179CrossRef
27.
Zurück zum Zitat Harris RK, Becker ED, Cabral de Menezes SM, Granger P, Hoffman RE, Zilm KW (2008) Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008) Solid State Nucl Mag Res 33(3):41–56CrossRef Harris RK, Becker ED, Cabral de Menezes SM, Granger P, Hoffman RE, Zilm KW (2008) Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008) Solid State Nucl Mag Res 33(3):41–56CrossRef
28.
Zurück zum Zitat Elena B, Lesage A, Steuernagel S, Böckmann A, Emsley L (2005) Proton to Carbon-13 INEPT in solid-state NMR spectroscopy. J Am Chem Soc 127(49):17296–17302CrossRef Elena B, Lesage A, Steuernagel S, Böckmann A, Emsley L (2005) Proton to Carbon-13 INEPT in solid-state NMR spectroscopy. J Am Chem Soc 127(49):17296–17302CrossRef
29.
Zurück zum Zitat Sørensen OW, Ernst RR (1969) Elimination of spectral distortion in polarization transfer experiments. Improvements and comparison of techniques. J Magn Reson 51(3):477–489 Sørensen OW, Ernst RR (1969) Elimination of spectral distortion in polarization transfer experiments. Improvements and comparison of techniques. J Magn Reson 51(3):477–489
30.
Zurück zum Zitat Bjoerling M, Karlstroem G, Linse P (1991) Conformational adaptation of poly (ethylene oxide): a 13C carbon NMR study. J Phys Chem 17(95):6706–6709CrossRef Bjoerling M, Karlstroem G, Linse P (1991) Conformational adaptation of poly (ethylene oxide): a 13C carbon NMR study. J Phys Chem 17(95):6706–6709CrossRef
31.
Zurück zum Zitat Sasanuma Y (1995) Conformational analysis of poly (propylene oxide) and its model compound 1,2-dimethoxypropane. Macromolecules 28:8629–8638CrossRef Sasanuma Y (1995) Conformational analysis of poly (propylene oxide) and its model compound 1,2-dimethoxypropane. Macromolecules 28:8629–8638CrossRef
32.
Zurück zum Zitat Ma J, Guo C, Tang Y, Wang J, Zheng L, Liang X, Chen S, Liu H (2006) Microenvironmental and conformational structure of triblock copolymers in aqueous solution by 1H and 13C NMR spectroscopy J Colloid Interf Sci 299(2):953–961CrossRef Ma J, Guo C, Tang Y, Wang J, Zheng L, Liang X, Chen S, Liu H (2006) Microenvironmental and conformational structure of triblock copolymers in aqueous solution by 1H and 13C NMR spectroscopy J Colloid Interf Sci 299(2):953–961CrossRef
33.
Zurück zum Zitat Wurtz P, Permi P, Nielsen NC, Sorensen OW (2008) Clean HMBC: suppression of strong-coupling induced artifacts in HMBC. J Magn Reson 194(1):89–98CrossRef Wurtz P, Permi P, Nielsen NC, Sorensen OW (2008) Clean HMBC: suppression of strong-coupling induced artifacts in HMBC. J Magn Reson 194(1):89–98CrossRef
34.
Zurück zum Zitat Mathias A, Mellor N (1966) Analysis of alkylene oxide polymers by nuclear magnetic resonance spectrometry and by gas-liquid chromatography Anal Chem 38(3):472–477CrossRef Mathias A, Mellor N (1966) Analysis of alkylene oxide polymers by nuclear magnetic resonance spectrometry and by gas-liquid chromatography Anal Chem 38(3):472–477CrossRef
35.
Zurück zum Zitat Randall Holmes–Farley S, Reamey RH, Mac Carthy JT, Deutch J, Whitesides GM (1985) Acid-base behavior of carboxylic acid groups covalently attached at the surface of polyethylene: the usefulness of contact angle in following the ionization of surface functionality. Langmuir 1(6):725–740CrossRef Randall Holmes–Farley S, Reamey RH, Mac Carthy JT, Deutch J, Whitesides GM (1985) Acid-base behavior of carboxylic acid groups covalently attached at the surface of polyethylene: the usefulness of contact angle in following the ionization of surface functionality. Langmuir 1(6):725–740CrossRef
36.
Zurück zum Zitat Liu CC, Marcel GE (1996) The fumed silica surface, a study by NMR. J Am Chem Soc 118:5103–5119CrossRef Liu CC, Marcel GE (1996) The fumed silica surface, a study by NMR. J Am Chem Soc 118:5103–5119CrossRef
37.
Zurück zum Zitat Baccile N, Laurent G, Bonhomme C, Innocenzi P, Babonneau F (2007) Solid-state NMR characterization of the surfactant−silica interface in templated silicas: acidic versus basic conditions. Chem Mater 19:1343–1354 Baccile N, Laurent G, Bonhomme C, Innocenzi P, Babonneau F (2007) Solid-state NMR characterization of the surfactant−silica interface in templated silicas: acidic versus basic conditions. Chem Mater 19:1343–1354
38.
Zurück zum Zitat Imperor-Clerc M, Davidson P, Davidson A (2000) Existence of a microporous corona around the mesopores of SBA-15 silica materials templated by triblock copolymers. J Am Chem Soc 122:11925–11933CrossRef Imperor-Clerc M, Davidson P, Davidson A (2000) Existence of a microporous corona around the mesopores of SBA-15 silica materials templated by triblock copolymers. J Am Chem Soc 122:11925–11933CrossRef
39.
Zurück zum Zitat Galarneau A, Cambon H, Di Renzo F, Fajula F (2001) True microporosity and surface area of mesoporous SBA- 15 silicas as a function of synthesis temperature. Langmuir 17(26):8328–8335CrossRef Galarneau A, Cambon H, Di Renzo F, Fajula F (2001) True microporosity and surface area of mesoporous SBA- 15 silicas as a function of synthesis temperature. Langmuir 17(26):8328–8335CrossRef
40.
Zurück zum Zitat Parmentier J, Saadhallah S, Reda M, Gibot L, Roux C, Vidal C, Vix-Guter C, Patarin J (2004) New carbons with controlled nanoporosity obtained by nanocasting using a SBA-15 mesoporous silica host matrix and different preparation routes. J Phys Chem Solids 65(2–3):139–146CrossRef Parmentier J, Saadhallah S, Reda M, Gibot L, Roux C, Vidal C, Vix-Guter C, Patarin J (2004) New carbons with controlled nanoporosity obtained by nanocasting using a SBA-15 mesoporous silica host matrix and different preparation routes. J Phys Chem Solids 65(2–3):139–146CrossRef
Metadaten
Titel
Stability and degradation of PEO20PPO70PEO20 triblock copolymers in mesostructured silica
verfasst von
Brindusa Dragoi
Guillaume Laurent
Sandra Casale
Taissire Benamor
Bénédicte Lebeau
Cédric Boissière
François Ribot
Mohamed Selmane
Patrick Schmidt
David Kreher
Anne Davidson
Publikationsdatum
29.06.2019
Verlag
Springer US
Erschienen in
Journal of Sol-Gel Science and Technology / Ausgabe 3/2019
Print ISSN: 0928-0707
Elektronische ISSN: 1573-4846
DOI
https://doi.org/10.1007/s10971-019-05044-w

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