Hydrolysis and condensation behavior of tetraethoxysilane, hexaethoxydisiloxane, and octaethoxytrisiloxane
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Abstract
Abstract In the initial stage of the hydrolysis–condensation of tetraethoxysilane (TEOS), hexaethoxydisiloxane (HEDS) and octaethoxytrisiloxane (OETS) are formed. However, little is known about the hydrolysis–condensation of HEDS and OETS. In this study, the hydrolysis–condensation of TEOS, HEDS, and OETS was investigated. HEDS and OETS were synthesized from diethoxy(diisocyanato)silane, a raw material with controllable functionality. The hydrolysis of TEOS, HEDS, and OETS was analyzed by mass spectroscopy, gel permeation chromatography, and nuclear magnetic resonance. The hydrolysis–condensation product of TEOS was a three-dimensional network-type polysiloxane. The hydrolysis–condensation product of HEDS consisted mainly of four-membered cyclic siloxane. The hydrolysis–condensation product of OETS consisted mainly of various membered cyclic siloxanes. Graphical Abstract
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Research context
OpenAlex topics: Silicone and Siloxane Chemistry · Marine Biology and Environmental Chemistry · Surface Modification and Superhydrophobicity
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References (53)
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1. Dislich H (1971) New routes to multicomponent oxide glasses. Angew Chem Int Ed Engl 10:363–370. https://doi.org/10.1002/anie.19710363110.1002/anie.197103631 ↗
2. Abe Y, Gunji T (2004) Oligo‐ and polysiloxanes. Prog Polym Sci 29:149–182. https://doi.org/10.1016/j.progpolymsci.2003.08.00310.1016/j.progpolymsci.2003.08.003 ↗
3. Cihlář J (1993) Hydrolysis and polycondensation of ethyl silicates. 1. Effect of pH and catalyst on the hydrolysis and polycondensation of tetraethoxysilane (TEOS). Colloids Surf A 70:239–251. https://doi.org/10.1016/0927-7757(93)80298-S10.1016/0927-7757(93)80298-S ↗
4. Harris MT, Brunson RR, Byers CH (1990) The base-catalyzed hydrolysis and condensation reactions of dilute and concentrated TEOS solutions. J Non Cryst Solids 121:397–403. https://doi.org/10.1016/0022-3093(90)90165-I10.1016/0022-3093(90)90165-I ↗
5. Tejedor-Tejedor MI, Paredes L, Anderson MA (1998) Evaluation of ATR−FTIR spectroscopy as an “in situ” tool for following the hydrolysis and condensation of alkoxysilanes under rich H2O conditions. Chem Mater 10:3410–3421. https://doi.org/10.1021/cm980146l10.1021/cm980146l ↗
6. Echeverría JC, Moriones P, Arzamendi G, Garrido JJ, Gil MJ, Cornejo A, Martínez-Merino V (2018) Kinetics of the acid-catalyzed hydrolysis of tetraethoxysilane (TEOS) by 29Si NMR spectroscopy and mathematical modeling. J Sol Gel Sci Technol 86:316–328. https://doi.org/10.1007/s10971-018-4637-710.1007/s10971-018-4637-7 ↗
7. Mazúr M, Mlynárik V, Valko M, Pelikán P (2000) The time evolution of the sol-gel process:29Si NMR study of the hydrolysis and condensation reactions of tetraethoxysilane. Appl Magn Reson 18:187–197. https://doi.org/10.1007/BF0316211010.1007/BF03162110 ↗
8. Brinker CJ (1988) Hydrolysis and condensation of silicates: Effects on structure. J Non Cryst Solids 100:31–50. https://doi.org/10.1016/0022-3093(88)90005-110.1016/0022-3093(88)90005-1 ↗
9. Depla A, Lesthaeghe D, Van Erp TS, Aerts A, Houthoofd K, Fan F, Li C, Speybroeck VVAN, Waroquier M, Kirschhock CEA, Martens JA (2011) 29Si NMR and UV−Raman investigation of initial oligomerization reaction pathways in acid-catalyzed silica sol−gel chemistry. J Phys Chem C 115:3562–3571. https://doi.org/10.1021/jp109901v10.1021/jp109901v ↗
10. Assink RA, Kay BD (1988) Sol-gel kinetics I. Functional group kinetics. J Non Cryst Solids 99:359–370. https://doi.org/10.1016/0022-3093(88)90441-310.1016/0022-3093(88)90441-3 ↗
11. Ueda N, Gunji T, Abe Y (2008) Syntheses of linear ethoxysiloxanes by the oxidative condensation of triethoxysilane. J Sol Gel Sci Technol 48:163–167. https://doi.org/10.1007/s10971-008-1808-y10.1007/s10971-008-1808-y ↗
12. Abe I, Sato Y, Hayami R, Yamamoto K, Tsukada S, Gunji T (2023) Oxidation of triethoxysilane by Wilkinson’s catalyst and its kinetic constants. Mater Technol in press.
13. Abe Y, Shimano R, Arimitsu K, Gunji T (2003) Preparation and properties of high molecular weight polyethoxysiloxanes stable to self-condensation by acid-catalyzed hydrolytic polycondensation of tetraethoxysilane. J Polym Sci A Polym Chem 41:2250–2255. https://doi.org/10.1002/pola.1073910.1002/pola.10739 ↗
14. Gunji T, Hayashi Y, Komatsubara A, Arimitsu K, Abe Y (2012) Preparation and properties of flexible free-standing films via polyalkoxysiloxanes by acid-catalyzed controlled hydrolytic polycondensation of tetraethoxysilane and tetramethoxysilane. Appl Organomet Chem 26:32–36. https://doi.org/10.1002/aoc.186110.1002/aoc.1861 ↗
15. Sanchez J, McCormick A (1992) Kinetic and thermodynamic study of the hydrolysis of silicon alkoxides in acidic alcohol solutions. J Phys Chem 96:8973–8979. https://doi.org/10.1021/j100201a05110.1021/j100201a051 ↗
16. Sanchez J, McCormick AV (1994) Intramolecular vs. intermolecular condensation rates in the acidic polymerization of octaethoxytrisiloxane. J Non Cryst Solids 167:289–294. https://doi.org/10.1016/0022-3093(94)90251-810.1016/0022-3093(94)90251-8 ↗
17. Lin CC, Basil JD (1986) 29Si NMR, sec and ftir studies of the hydrolysis and condensation of Si(OC2H5)4 and Si2O(OC2H5)6. Mater Res Soc Symp Proc 73:585–590. https://doi.org/10.1557/PROC-73-58510.1557/PROC-73-585 ↗
18. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams-Young D, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ (2016) Gaussian˜16 Revision C.01
19. Abe Y, Motoyama K, Kobayashi T, Iwasaki S, Gunji T (1996) Syntheses of Alkoxyisocyanatosilanes from Tri- and Tetraisocyanatosilane. Nippon Kagaku Kaishi 1996:969–974. https://doi.org/10.1246/nikkashi.1996.96910.1246/nikkashi.1996.969 ↗
20. Kazakova VV, Gorbatsevich OB, Skvortsova SA, Demchenko NV, Muzafarov AM (2005) Synthesis of triethoxysilanol. Russ Chem Bull 54:1350–1351. https://doi.org/10.1007/s11172-005-0409-y10.1007/s11172-005-0409-y ↗
21. Yamamoto K, Shimoda T, Sato Y, Nakaya T, Ohshita J, Gunji T (2022) Preparation and film properties of polysiloxanes consisting of di- and quadra-functional hybrid units. J Sol Gel Sci Technol 104:724–734. https://doi.org/10.1007/s10971-022-05806-z10.1007/s10971-022-05806-z ↗
22. Abe Y, Kanemaru T, Yamazaki T, Nagao Y, Misono T (1991) The reaction of isocyanatosilanes with ethanol and synthesis of their derivatives. Nippon Kagaku Kaishi 1991:1094–1101. https://doi.org/10.1246/nikkashi.1991.109410.1246/nikkashi.1991.1094 ↗
23. Kondo Y, Miyao K, Aya Y, Yoshino (2004) N synthesis of and glass surface modification with fluorinated silane coupling agents with a benzene ring as a spacer. J Oleo Sci 53:143–151. https://doi.org/10.5650/jos.53.14310.5650/jos.53.143 ↗
24. Sakurai H, Nozaki H, Yamamoto S, Tsuji J, Noyori R (1985) Application of organosilicon compounds to organic synthesis, 105. Kagaku Dojin (Japan), pp. 33–40
25. Corriu RJP, Guerin C (1982) Nucleophilic displacement at silicon: recent developments and mechanistic implications. Adv Organomet Chem 265–312. https://doi.org/10.1016/S0065-3055(08)60523-710.1016/S0065-3055(08)60523-7 ↗
26. Gunji T, Setogawa A, Asakura K, Abe Y (1998) Syntheses and properties of isocyanatodisiloxanes and their alkoxy-substituted derivatives. Bull Chem Soc Jpn 71:2967–2972. https://doi.org/10.1246/bcsj.71.296710.1246/bcsj.71.2967 ↗
27. Oberhammer H, Boggs JE (1980) Importance of (p-d).pi. bonding in the siloxane bond. J Am Chem Soc 102:7241–7244. https://doi.org/10.1021/ja00544a01110.1021/ja00544a011 ↗
28. Dankert F, Hänisch C (2021) Siloxane coordination revisited: Si−O bond character, reactivity and magnificent molecular shapes. Eur J Inorg Chem 2021:2907–2927. https://doi.org/10.1002/ejic.20210027510.1002/ejic.202100275 ↗
29. Abe Y, Ito A, Hisano Y, Nagao Y, Misono T (1992) Synthesis and Properties of Polysilazanes from Phenyltriisocyanatosilane. NIPPON KAGAKU KAISHI 1992:649–656. https://doi.org/10.1246/nikkashi.1992.64910.1246/nikkashi.1992.649 ↗
30. Kozyukov VP, Sheludyakov VD, Mironov VF (1973) Russian Chem. Rev 42:662–677. https://doi.org/10.1070/RC1973v042n08ABEH00270410.1070/RC1973v042n08ABEH002704 ↗
31. Jensen JO (2003) Vibrational frequencies and structural determinations of tetraisocyanatosilane. Spectrochim Acta Part A 59:937–947. https://doi.org/10.1016/S1386-1425(02)00280-910.1016/S1386-1425(02)00280-9 ↗
32. Miller FA, Carlson GL (1961) The vibrational spectra and structure of Si(NCO)4 and Ge(NCO)4. Spectrochim Acta 17:977–989. https://doi.org/10.1016/0371-1951(61)80033-710.1016/0371-1951(61)80033-7 ↗
33. Newton WE, Rochow EG (1970) Vibrational spectra of some trialkoxysilanes. J Chem Soc A 1970:2664–2668. https://doi.org/10.1039/J1970000266410.1039/J19700002664 ↗
34. Sato Y, Hayami R, Gunji T (2022) Characterization of NMR, IR, and Raman spectra for siloxanes and silsesquioxanes: a mini review. J Sol Gel Sci Technol 104:36–52. https://doi.org/10.1007/s10971-022-05920-y10.1007/s10971-022-05920-y ↗
35. Rubio F, Rubio J, Oteo JL (1998) A FT-IR study of the hydrolysis of tetraethylorthosilicate (TEOS). Spectrosc Lett 31:199–219. https://doi.org/10.1080/0038701980800677210.1080/00387019808006772 ↗
36. Kay BD, Assink RA (1988) Sol-gel kinetics: II. Chemical speciation modeling. J Non Cryst Solids 104:112–122. https://doi.org/10.1016/0022-3093(88)90189-510.1016/0022-3093(88)90189-5 ↗
37. Gunji T (1992) Tokyo University of Science, Doctoral dissertations "Studies of the synthesis of metalloxanes and their characterization as ceramic precursors", p110. https://doi.org/10.11501/307119610.11501/3071196 ↗
38. Gunji T, Sopyan I, Abe Y (1994) Synthesis of polytitanosiloxanes and their transformation to SiO2–TiO2 ceramic fibers. J Polym Sci A Polym Chem 32:3133–3139. https://doi.org/10.1002/pola.1994.08032161310.1002/pola.1994.080321613 ↗
39. Lentz CW (1964) Silicate minerals as sources of trimethylsilyl silicates and silicate structure analysis of sodium silicate solutions. Inorg Chem 3:574–579. https://doi.org/10.1021/ic50014a02910.1021/ic50014a029 ↗
40. Flagg DH, Mccarthy TJ (2016) Rediscovering silicones: MQ copolymers. Macromolecules 49:8581–8592. https://doi.org/10.1021/acs.macromol.6b0185210.1021/acs.macromol.6b01852 ↗
41. Liang W, Ge X, Ge J, Li T, Zhao T, Chen X, Song Y, Cui Y, Khan M, Ji J, Pang X, Liu R (2018) Reduced graphene oxide embedded with MQ silicone resin nano-aggregates for silicone rubber composites with enhanced thermal conductivity and mechanical performance. Polymers 10:1254. https://doi.org/10.3390/polym1011125410.3390/polym10111254 ↗
42. Cruz-Quesada G, Espinal-Viguri M, López-Ramón M, Garrido J (2022) Novel silica hybrid xerogels prepared by co-condensation of TEOS and ClPhTEOS: a chemical and morphological study. Gels 8:677. https://doi.org/10.3390/gels810067710.3390/gels8100677 ↗
43. Klemperer WG, Mainz VV, Ramamurthi SD, Rosenberg FS (1988) Structural characterization of polysilicate intermediates formed during sol-gel polymerization. Mater Res Soc Symp Proc 121:15–24. https://doi.org/10.1557/PROC-121-1510.1557/PROC-121-15 ↗
44. Brus J, Karhan J, Kotlík P (1996) 29Si NMR study of distribution of oligomers in polycondensation of tetraethoxysilane. Collect Czech Chem Commun 61:691–703. https://doi.org/10.1135/cccc1996069110.1135/cccc19960691 ↗
45. Hook RJ (1996) A 29Si NMR study of the sol-gel polymerisation rates of substituted ethoxysilanes. J Non Cryst Solids 195:1–15. https://doi.org/10.1016/0022-3093(95)00508-010.1016/0022-3093(95)00508-0 ↗
46. Ueda N, Gunji T, Abe Y (2008) Synthesis of alkoxy octasilsesquioxanes by a convenient one-pot reaction. Mater Technol 26:162–169
47. Hayami R, Wada K, Nishikawa I, Sagawa T, Yamamoto K, Tsukada S, Gunji T (2017) Preparation and properties of organic–inorganic hybrid materials using titanium phosphonate cluster. Polym J 49:665–669. https://doi.org/10.1038/pj.2017.3410.1038/pj.2017.34 ↗
48. Kelts LW, Armstrong NJ (1989) A silicon-29 NMR study of the structural intermediates in low pH sol-gel reactions. J Mater Res 4:423–433. https://doi.org/10.1557/JMR.1989.042310.1557/JMR.1989.0423 ↗
49. Myers SA, Assink RA, Loy DA, Shea KJ (2000) Investigation of the transmission of substituent effects by 29Si NMR. J Chem Soc Perkin Trans 2:545–549. https://doi.org/10.1039/A906569E10.1039/A906569E ↗
50. Saito H, Nishio Y, Kobayashi M, Sugahara Y (2011) Hydrolysis behavior of a precursor for bridged polysilsesquioxane 1,4–bis (triethoxysilyl) benzene: a 29Si NMR study. J Sol Gel Sci Technol 57:51–56. https://doi.org/10.1007/s10971-010-2323-510.1007/s10971-010-2323-5 ↗
51. Yamamoto K, Saito I, Amaike Y, Nakaya T, Oshita J, Gunji T (2023) Gel structure and water desalination properties of divinylpyrazine-bridged polysilsesquioxanes. J Sol Gel Sci Technol, https://doi.org/10.1007/s10971-022-06017-210.1007/s10971-022-06017-2 ↗
52. McIntosh GJ (2013) Theoretical investigations into the nucleation of silica growth in basic solution part I–ab Initio studies of the formation of trimers and tetramers. Phys Chem Chem Phys 15:3155–3172. https://doi.org/10.1039/C3CP43399D10.1039/C3CP43399D ↗
53. Gunji T, Nagao Y, Misono T, Abe Y (1992) Condensation and structure of silicic acid in tetrahydrofuran. J Polym Sci A Polym Chem 30:1779–1787. https://doi.org/10.1002/pola.1992.08030090110.1002/pola.1992.080300901 ↗