Abstract
Low-density organic aerogels (down to 11–12 mg/cm3) were successively synthesized by polycondensation of formaldehyde with bisphenol A (2,2-diphenylolpropane or BPhA) methylol derivatives by the thermal treatment under basic conditions. In this paper, the main features of bisphenol A-formaldehyde (BF) sol and hydrogel formation have been examined for the first time. The molecular weight distribution both of the initial resin and the soluble products of its thermal processing were studied by size exclusion chromatography. A detailed study of the structure of sols and the dynamics of its change was carried out by dynamic and static light scattering and scanning and transmission electron microscopy. The results obtained allowed to describe the process of gel formation as a diffusion-limited cluster-cluster fractal aggregation of sol nanoparticles formed during the polycondensation. Crosslinking of low-density fractal aggregates leads to the formation of a macro-porous structure with a high pore volume and, ultimately, to a low-density aerogel.
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Fricke J, Emmerling A (1998) Aerogels–recent progress in production techniques and novel applications. J Sol-Gel Sci Technol 13:299–303. https://doi.org/10.1023/A:100866390
Akimov YK (2003) Fields of application of aerogels. Instrum Exp Tech 46:287–299. https://doi.org/10.1023/A:1024401803057
Smirnov BM (1987) Aerogels. Sov Phys Uspekhi 30:420–432. https://doi.org/10.1070/PU1987v030n05ABEH002906
Orekhov AS, Akunets AA, Borisenko LA, Gromov AI, Merkuliev YA, Pimenov VG, Sheveleva EE, Vasiliev VG, Borisenko NG (2016) Modern trends in low-density materials for fusion. J Phys Conf Ser 688:012080. https://doi.org/10.1088/1742-6596/688/1/012080
Barral K (1998) Low-density organic aerogels by double-catalysed synthesis. J Non-Cryst Solids 225:46–50. https://doi.org/10.1016/S0022-3093(98)00007-6
Sveс F (2010) Porous polymer monoliths: amazingly wide variety of techniques enabling their preparation. J Chromatogr A 1217:902–924. https://doi.org/10.1016/j.chroma.2009.09.073
Tikhonov VE, Blagodatskikh IV, Postnikov VA, Klemenkova ZS, Vyshivannaya OV, Khokhlov AR (2016) New approach to the synthesis of a functional macroporous poly(vinylalcohol) network and design of boronate affinity sorbent for protein separation. Eur Polym J 75:1–12. https://doi.org/10.1016/j.eurpolymj.2015.11.035
Nischang I (2013) Porous polymer monoliths: morphology, poros properties, polymer nano-scale gel structure and their impact on chromatographic performance. J Chromatogr A 26:39–58. https://doi.org/10.1016/j.chroma.2012.11.016
Einarsrud MA, Nilsen E (1998) Strengthening of water glass and colloidal sol based silica gels by aging in TEOS. J Non-Cryst Solids 226:122–128. https://doi.org/10.1016/S0022-3093(98)00370-6
Kocon L, Despetis F, Phalippou J (1998) Ultralow density silica aerogels by alcohol supercritical drying. J Non-Cryst Solids 225:96–100. https://doi.org/10.1016/S0022-3093(98)00322-6
Shabanova NA, Sarkisov PD (2012) Sol-gel technologies. Nanodisperse silica. Binominal. Laboratory of Knowledge, Moscow
Durairaj RB (2005) Resorcinol. Chemistry, technology and application. Springer-Verlag, Berlin
Mitsunaga T, Conner AH, Hill Jr CG (2002) Predicting the hydroxymethylation rate of phenols with formaldehyde by molecular orbital calculation. J Wood Sci 48:153–158. https://doi.org/10.1007/BF00767293
Knop A, Louis AP, Volker B (2014) Phenolic resins: chemistry, applications and performance. Springer Science & Business Media, New York
Kobayashi S, Itoh H (2002) Pat 6,379,862 USA
Harris TG (1982) Pat 4,357,457 USA
Nobuyuoki T, Tadao I (1980) Pat. 55-64537A Japan
Kondratiev VP, Kondrashchenko VI (2004) Synthetic glues for wood materials. The Scientific World, Moscow
Sheveleva EE, Pimenov VG, Pikulin IV, Sakharov AM (2016) The formation of ultralow-density microcellular diane-formaldegyde gels and aerogels. Polymer Sci Ser B 58:173–182. https://doi.org/10.1134/S1560090416020081
Sorensen CM (2001) Light scattering by fractal aggregates: a review. Aerosol Sci Technol 35:648–687. https://doi.org/10.1080/02786820117868
Bushell GC, Yan YD, Woodfield D, Raper J, Amal R (2002) On techniques for the measurement of the mass fractal dimension of aggregates. Adv Colloid Interf Sci 95:1–50. https://doi.org/10.1016/S00018686(00)00078-6
Wu D, Fu R, Sun Z, Yu Z (2005) Low-density organic and carbon aerogels from the sol–gel polymerization of phenol with formaldehyde. J Non-Cryst Solids 351:915–921. https://doi.org/10.1016/j.jnoncrysol.2005.02.008
Ruben GC, Pekala RW, Tillotson TM, Hrubesh LW (1992) Imaging aerogels at the molecular level. J Mater Sci 27:4341–4349. https://doi.org/10.1007/BF00541564
Pekala RW (1989) Organic aerogels from the polycondensation of resorcinol with formaldegyde. J Mater Sci 24:3221–3227. https://doi.org/10.1007/BF0113904
Aegerter MA, Prassas M (2011) Aerogels Handbook. Springer, New York
Kätzel U, Vorbau M, Stintz M, Gottschalk-Gaudig T, Barthel H (2008) Dynamic light scattering for the characterization of Polydisperse fractal systems: II. Relation between structure and DLS results. Part Part Syst Charact 25:19–30. https://doi.org/10.1002/ppsc.200700005
Fernández-Nieves A, Fernández-Barbero A, de las Nieves FJ (2004) Static light scattering from fractal aggregates of microgel particles. Progr Colloid Polym Sci 123:251–254. https://doi.org/10.1007/978-3-540-36462-7_54
Zhou ZP, Wu P, Chu B (1991) Cationic surfactant induced fractal silica aggregates: a light-scattering study. J Colloid Interface Sci 146:541–555. https://doi.org/10.1016/0021-9797(91)90218-W
Freeman JH, Lewis CW (1954) Alkaline-catalyzed reaction of formaldehyde and the methylols of phenol; a kinetic study. J Am Chem Soc 76:2080–2087. https://doi.org/10.1021/ja01637a014
Acknowledgements
The authors are grateful to Department of Structural Research of the N.D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences for the study of samples by the method of electronic microscopy.
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This study was performed with financial support of the Russian Science Foundation (Grant No. 14-50-00126).
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Sheveleva, E.E., Pimenov, V.G., Blagodatskikh, I.V. et al. Synthesis, structure, and properties of bisphenol A formaldehyde sol—precursor of low-density aerogel. Colloid Polym Sci 296, 1313–1322 (2018). https://doi.org/10.1007/s00396-018-4343-6
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DOI: https://doi.org/10.1007/s00396-018-4343-6