Sol-gel polycondensation kinetic modeling: methylethoxysilanes

AIChE Journal

Volumn 44, Issue 5, 1998, Pages 1141-1156

  Rankin, Stephen E ^a   Macosko, Christopher W ^a   McCormick, Alon V ^a  

^a University of Minnesota   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

HYDROLYSIS; MATHEMATICAL MODELS; MOLECULAR STRUCTURE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYCONDENSATION; REACTION KINETICS; SOL-GELS;

METHYLETHOXYSILANES;

SILANES;

EID: 0032075328     PISSN: 00011541     EISSN: None     Source Type: Journal    
DOI: 10.1002/aic.690440512     Document Type: Article

References (94)

1. Alam, T. M., R. A. Assink, and D. A. Loy, "Hydrolysis and Esterification in Organically Modified Alkoxysilanes: A Si NMR Investigation of Methyltrimethoxysilane," Chem. Mater., 8, 2366 (1996a).
2. Alam, T. M., R. A. Assink, S. Prabakar, and D. A. Loy, "Identification and Characterization of the Hydrolysis Products in TMOS and MTMS Monomers using Si-29 NMR and Polarization Transfer Techniques," Magn. Reson. Chem., 34, 603 (1996b).
3. Assink, R. A., and B. D. Kay, "Sol-Gel Kinetics I. Functional Group Kinetics,"J. Non-Cryst. Sol., 99, 359 (1988a).
4. Assink, R. A., and B. D. Kay, "Sol-Gel Kinetics HI. Test of the Statistical Reaction Model,"J. Non-Cryst. Solids, 107, 35 (1988b).
5. Assink, R. A., and B. D. Kay, "The Chemical Kinetics of Silicate Sol-Gels: Functional Groups Kinetics of Tetraethoxysilane," Colloids Surf. A, 74, 1 (1993).
6. Bailey, J. K., C. W. Macosko, and M. L. Mecartney, "Modeling the Gelation of Silicon Alkoxides,"J. Non-Cryst. Solids, 125,208 (1990).
7. Baney, R. H., M. Itoh, A. Sakakibara, and T. Suzuki, "Silsesquioxanes," Chem. Rev., 95, 1409 (1995).
8. Barry, A. J., and H. N. Beck, "Silicone Polymers," Inorganic Polymers, F. G. A. Stone and W. A. G. Graham, eds., Academic Press, New York (1962).
9. Brinker, C. J., and R. A. Assink, "Spinnability of Silica Sols. Structural and Rheological Criteria,"J. Non-Cryst. Solids, 111, 48 (1989).
10. Brinker, C. J., and G. W. Scherer, Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing, Academic Press, Boston (1990).
11. Brunei, F., and B. Cabane, "Populations of Oligomers in Sol-Gel Condensation,"J. Non-Cryst. Solids, 163, 211 (1993).
12. Brus, J., J. Karhan, and P. Kotlik, "29Si NMR Study of Distribution of Oligomers in Polycondensation of Tetraethoxysilane," Collect. Czech. Chem. Commun., 61, 691 (1996).
13. Brus, J., and P. Kotlik, "Polyacrylate Effects on Tetraethoxysilane Polycondensation," Chem. Mater., S, 2739 (1996).
14. Cardenas, A., N. Hovnanian, and M. Smaihi, "Sol-Gel Formation of Heteropolysiloxanes from Diethylhphosphatoethyltriethoxysilane and Tetraethoxysilane," J. Appl. Polym. Sei., 60, 2279 (1996).
15. Chambers, R, C., J. W. E. Jones, Y. Haruvy, S. E. Webber, and M. A. Fox, "Influence of Steric Effects on the Kinetics of Ethyltrimethoxysilane Hydrolysis in a Fast Sol-Gel System," Chem. Mater., 5, 1481 (1993).
16. Chojnowski, J., M. Cypryk, K. Kazmierski, and K. Rôzga, "The Reactivity of Monomeric Silanol Intermediates in the Hydrolysis Polycondensation of Tetraethoxysilane in Acidic Media," J. NonCryst. Solids, 125, 40 (1990).
17. Chojnowski, J., M. Scibiorek, and J. Kowalski, "Mechanism of the Formation of Macrocycles During the Cationic Polymerization of Cyclotrisiloxanes. End to End Ring Closure Versus Ring Expansion," Makromol. Chem., 178, 1351 (1977).
18. Cihlâr, J., "Hydrolysis and Polycondensation of Ethyl Silicates. 1. Effect of pH and Catalyst on the Hydrolysis and Polycondensation of Tetraethoxysilane," Coll. Surf. A, 70, 239 (1993).
19. Clark, T., A Handbook of Computational Chemistry, Wiley, New York (1985).
20. Clarson, S. J., and J. A. Semlyen, Siloxane Polymers, Prentice Hall, Englewood Cliffs, NJ (1993).
21. DeLattre, L., and F. Babonneau, "Influence of the Nature of the R Group on the Hydrolysis and Condensation Process of Trifunctional Silicon Alkoxides, R-Si(OR')j," Better Ceramics Through Chemistry VI, A. K. Cheetham, C. J. Brinker, M. L. McCartney, and C. Sanchez, eds., Materials Research Society, Pittsburgh, p. 365 (1994).
22. DeLattre, L., M. Roy, and F. Babonneau, "Design of Homogeneous Hybrid Materials Through a Careful Control of the Synthetic Procedure,"J. Sol-Gel Sei. Technol., S, 567 (1997).
23. Devreux, F., J. P. Boilot, and F. Chaput, "Sol-Gel Condensation of Rapidly Hydrolyzed Silicon Alkoxides: A Joint 29Si NMR and Small-Angle X-Ray Scattering Study," Phys. Reu. A, 41, 6901 (1990).
24. De Witte, B. M., D. Commers, and J. B. Uytterhoeven, "Distribution of Organic Groups in Silica Gels Prepared from Organo-AIkoxysilanes,"J. Non-Ciyst. Solids, 202, 35 (1996).
25. Dotson, N. A., R. Galvan, R. L. Laurence, and M. Tirrell, Polymerization Process Modeling, VCH, New York (1996).
26. Doughty, D. H., R. A. Assink, and B. D. Kay, "Hydrolysis and Condensation Kinetics of Dimeric Sol-Gel Species by ^Si NMR Spectroscopy," Silicon-Based Polymer Science: A Comprehensive Resource, J. M. Zeigler, and F. W. G. Feuron, eds., ACS, Washington, DC, p. 241 (1990).
27. Fyfe, C. A., and P. P. Aroca, "Quantitative Kinetic Analysis by High-Resolution 29Si NMR Spectroscopy of the Initial Stages in the Sol-Gel Formation of Silica Gel from Tetraethoxysilane," Chem. Mater., 7, 1800 (1995).
28. Gordon, M., and W. B. Temple, "The Graph-Like State of Molecules HI. Ring-Chain Competition Kinetics in Linear Polymerisation Reactions," Makromol. Chem., 160, 263 (1972).
29. Grubb, W. T., "A Rate Study of the Silanol Condensation Reaction at 25° in Alcoholic Solvents,"J. Amer. Chem. Soc., 76, 3408 (1954).
30. Guibergia-Pierron, M., and G. Sauvet, "Heterofunctional Condensation of Alkoxysilanes and Silanols-I. Synthesis of Definite Polysiloxane Networks," Ear. Poly. J., 28, 29 (1992).
31. Harris, R. K., Nuclear Magnetic Resonance Spectoscopy. A PhysicoChemical Vmv, Wiley, New York (1986).
32. Harris, R. K., and M. L. Robins, "29Si Nuclear Magnetic Resonance Studies of Oligomeric and Polymeric Siloxanes: 4. Chemical Shift Effects of End-Groups," Polymer, 19, 1123 (1978).
33. Helary, G., and G. Sauvet, "Heterofunctional Condensation of Alkoxysilanes and Silanols-II. Synthesis of Linear Poly(aminoalkylsiloxane)s," Eur. Pofy. J., 28, 37 (1992).
34. Hook, R. J., "A 29Si NMR Study of the Sol-Gel Polymerisation Rates of Substituted Ethoxysilanes," J. Non-Cryst. Solids, 195, 1 (1996).
35. Hoshino, Y., and J. D. Mackenzie, "Viscosity and Structure of Ormosil Solutions,"J. Sol-Gel. Sei. Technol., 5, 83 (1995).
36. Her, R. K., Tlie Chemistry of Silica, Wiley, New York (1979).
37. Kasehagen, L. J., S. E. Rankin, A. V. McCormick, and C. W. Macosko, "Modeling FSSE and Preferred Cyclization in Sol-Gel Polymerization," Macromol., 30, 3921 (1997).
38. Kazmierski, K., J. Chojnowski, and J. McVie, "The Acid-Catalyzed Condensation of Methyl Substituted Model Oligosiloxanes Bearing Silanol and Ethoxysilane Functions," Eur. Poly. J., 30, 515 (1994).
39. Kelling, H., K. Lange, and A. Surkus, "On the Acid-Catalyzed Reaction of Siloxanes with Alcohols," Organosilicon Chemistry. From Molecules to Materials, N. Aubert and J. Weis eds., VCH, Weinheim, p. 67 (1994).
40. Kelts, L. W., and N. J. Armstrong, "A Silicon-29 NMR Study of the Structural Intermediates in low pH Sol-Gel Reactions," J. Mater. Res., 4, 423 (1989).
41. Kirn, J., J. L. Plawskey, E. Van Wagenen, and G. M. Korenowski, "Effect of Processing Parameters and Polymerization Behavior on the Nonlinear Optical Response of Sol-Gel Materials," Chem. Mater., 5, 1118 (1993).
42. Klemperer, W. G., and S. D. Ramamurthi, "A Flory-Stockmayer Analysis of Silica Sol-Gel Polymerization,"J. Non-Cryst. Solids, 121, 16 (1990).
43. Kumar, A., and S. Misra, "A Kinetic Approach to Multifunctional Polymerization with Cyclization," Pofy. Sei. Eng., 26, 1297 (1986).
44. Lasocki, Z., "Substitution at a Silicon Atom in Organosilicon Compounds: I. Rates of Condensation of Straight-Chain Alkyl Substituted Silanediols," Bull. Acad. Polon. Sei., Sér. Sei. Chim., 11, 637 (1963).
45. Lasocki, Z., "Substitution at a Silicon Atom in Organosilicon Compounds: II. Rates of Condensation of Branched-Chain Alkyl-Substituted Silanediols," Bull. Acad. Polon. Sei., Sér. Sei. Chim., 12, 223 (1964a).
46. Lasocki, Z., "Substitution at a Silicon Atom in Organosilicon Compounds: III. Steric and Polar Effects of Alkyl Groups in the Condensation of Silanediols," Bull. Acad. Polon. Sei., Sér. Sei. Chim., 12, 227 (1964b).
47. Ling, D. A., "Primary Structural Evolution in Acid-Catalyzed Silica Polysol-Gel Processes," PhD Thesis, Georgia Institute of Technology, Atlanta (1992).
48. Liu, J., and S. D. Kirn, "Polycondensation Behavior of Methyltrimethoxysilane Studied by NMR Spectroscopy," J. Poly. Sei. B: Pofym. Phys., 34, 131 (1996).
49. Lux, P., F. Brunei, J. Virlet, and B. Cabane, "Combined DEPT ID and INEPT DQF COSY 2D Experiments in wSi NMR Spectroscopy of Alkoxysilane Polymers 2," Magn. Reson. Chem., 34, 173 (1996).
50. Maas, U., and S. B. Pope, "Simplifying Chemical Kinetics: Intrinsic Low-Dimensional Manifolds in Composition Space," Combust. Flame, 88, 239 (1992).
51. Mark, J. E., C. Y.-C. Lee, and P. A. Bianconi, eds., Hybrid Inorganic-Organic Composites, ACS Symp. Ser., Vol. 585, American Chemical Society, Washington, DC (1995).
52. Marsmann, H., "29Si-NMR Spectroscopic Results," NMR: Basic Principles and Progress, P. Diehl E. Fluck, H. Günther, R. Dosfeld, and J. Seelig, eds., Springer-Verlag, Berlin, p. 65 (1981).
53. Ng, L. V., and A. V. McCormick, "Acidic Sol-Gel Polymerization of TEOS: Effect of Solution Composition on Cyclization and Bimolecular Condensation Rates,"J. Phys. Chem., 100, 12517 (1996).
54. Ng, L. V., P. Thompson, J. Sanchez, C. W. Macosko, and A. V. McCormick, "Formation of Cagelike Intermediates from Nonrandom Cyclization During Acid-Catalyzed Sol-Gel Polymerization of Tetraethyl Orthosilicate," Macromol., 28, 6471 (1995).
55. Osterholtz, F. D., and E. R. Pohl, "Kinetics of the Hydrolysis and Condensation of Organofunctional Alkoxysilanes: A Review," Silanes and Other Coupling Agents, K. L. Mittal, ed., VSP, Utrecht, The Netherlands, p. 119 (1992).
56. Peppas, N. A., A. B. Scranton, A. H. Tsou, and D. E. Edwards, "Branching Theory in Sol-Gel Processing," Better Ceramics Through Chemistry HI, C. J. Brinker, D. E. Clark, and D. R. Ulrich, eds., Materials Research Society, Pittsburgh, p. 43 (1988).
57. Pohl, E. R., and F. D. Osterholtz, "Kinetics and Mechanism of Aqueous Hydrolysis and Condensation of Alkyltrialkoxysilanes," Molecular Characterization of Composite Interfaces, H. Ishida and G. Kumar, eds., Plenum, New York, p. 157 (1985).
58. Pohl, E. R., arid F. D. Osterholtz, "Kinetics and Mechanism of Condensation of Alkylsilanols in Aqueous Solution," Silanes, Surfaces, and Interfaces, D. E. Leyden, eds., Gordon & Breach, New York, p. 481 (1986).
59. Pouxviel, J. C., and J. P. Boilot, "Kinetic Simulations and Mechanisms of the Sol-Gel Polymerization,"J. Non-Cryst. Solids, 94, 374 (1987).
60. Pouxviel, J. C., J. P. Boilot, J. C. Beloeil, and J. Y. Lallemand, "NMR Study of the Sol/Gel Polymerization,"J. Non-Cryst. Solids, 89, 345 (1987).
61. Prabakar, S., and R. A. Assink, "Hydrolysis and Condensation Kinetics of Two Component Organically Modified Silica Sols," J. NonCryst. Solids, 211, 39 (1997).
62. Rankin, S. E., C. W. Macosko, and A. V. McCormick, "Sol-Gel Kinetics for the Preparation of Inorganic/Organic Siloxane Copolymers," Better Ceramics Tlirough Chemistry VII, B. K. Coltrain, C. Sanchez, D. W. Schaefer and G. L. Wilkes, eds., Materials Research Society, Pittsburgh, p. 113 (1996).
63. Rankin, S. E., C. W. Macosko, and A. V. McCormick, "Copolymerization Kinetics of a Model Siloxane System,"J. Pofy. Sei. A, 35, 1293 (1997).
64. Rankin, S. E., C. W. Macosko, and A. V. McCormick, "Difficulties in Identifying Rate Parameters for Sol-Gel Modeling: Sensitivities and Experimental Signatures," (1998a).
65. Rankin, S. E., J. Sefcfk, and A. C. McCormick, "Sol-Gel Thermodynamics: II. Similarities in the Hydrolysis Pseudoequilibrium Behavior of Multifunctional Ethoxysilane Systems," (1998b).
66. Re, N., "Kinetics of Bicomponent Sol-Gel Processes,"J. Non-Ciyst. Solids, 142, 1 (1992).
67. Rolando, R. J., and C. W. Macosko, "Ring Formation in Linear Stepwise Polymerization," Macromol., 20, 2707 (1987).
68. Rühlmann, K., U. Scheim, and K. Käppier, "Substituent Constants for Groups at the Si-Atom," Progress in Organosilicon Chemistry, B. Marciniec and J. Chojnowski, eds., Gordon & Breach, Basel, Switzerland, p. 147 (1995).
69. Sanchez, J., and A. McCormick, "Kinetic and Thermodynamic Study of the Hydrolysis of Silicon Alkoxides in Acidic Alcohol Solutions," J. Phys. Cliem., 96, 8973 (1992a).
70. Sanchez, J., and A. McCormick, "Kinetics and Equilibrium of AcidCatalyzed Tetraethoxysilane Hydrolysis," Chemical Processing of Advanced Materials, L. L. Hench and J. K. West, eds., Wiley, New York, p. 43 (1992b).
71. Sanchez, J., and A. V. McCormick, "Intramolecular vs. Intermolecular Condensation Rates in the Acidic Polymerization of Octaethoxytrisiloxane," J. Non-Ciyst. Solids, 167, 289 (1994).
72. Sanchez, J., S. E. Rankin, and A. V. McCormick, "29Si NMR Kinetic Study of Tetraethoxysilane and Ethyl-Substituted Ethoxysilane Polymerization in Acidic Conditions," Ind. Eng. Chem. Res., 34, 117 (1996).
73. Sarmoria, C., and D. R. Miller, "Models for the First Shell Substitution Effect in Stepwise Polymerization," Macromol, 24,1833 (1991).
74. Sarmoria, C, E. M. Vallès, and D. R. Miller, "Validity of Some Approximation Used to Model Intramolecular Reaction in Irreversible Polymerization," Macromol., 23, 580 (1990).
75. Schaefer, D. W., G. L. Wilkes, C. Sanchez, and B. Coltrain, eds., Better Ceramics through Chemistry VII, Mat. Res. Soc. Symp. Proc., Materials Research Society, Pittsburgh (1996).
76. Schmidt, H., H. Scholze, and A. Kaiser, "Principles of Hydrolysis and Condensation Reaction of Alkoxysilanes,"J. Non-Cryst. Solids, 63, 1 (1984).
77. Sefcfk, J., and A. V. McCormick, "Kinetic and Thermodynamic Issues in Sol-Gel Processes Using Silicon Alkoxides," Catal. Today, 35, 205 (1997a).
78. Sefcfk, J., and A. V. McCormick, "Thermochemistry of Aqueous Sili-v cate Solution Precursors to Ceramics," AIChEJ., 43, 2773 (1997b).
79. Sefcfk, J., S. E. Rankin, S. J. Kirchner, and A. V. McCormick, "Silanol Esterification, Condensation, and Deprotonation Equilibria," (1998).
80. Smith, K. A., "A Study of the Hydrolysis of Methoxysilanes in a Two-Phase System," J. Org. Chem., 51, 3827 (1986).
81. Smith, K. A., "Polycondensation of Methyltrimethoxysilane," Macromol., 20, 2514 (1987).
82. Stanford, J. L., R. F. T. Stepto, and D. R. Waywell, "Rate Theory of Irreversible Linear Random Polymerisation: 2. Application to Intramolecular Reaction in A-A+B -B Type Polymerisations," J. Chem. Soc. Farad. Trans. I, 71, 1308 (1975).
83. Stepto, R. F. T., "Intra-Molecular Reaction and Gelation in Condensation or Random Polymerisation," NetH-ork Formation and Cyclisation in Polymer Reactions, R. N. Haward, ed., Applied Science Publishers, London, p. 81 (1981).
84. Stewart, J. J. P., "MOPAC: A Semiempirical Molecular Orbital Program,"J. Compta. Aided Mol. Des., 4, l (1990).
85. Sugahara, Y., S. Okada, K. Kuroda, and C. Kato, <<29Si-NMR Study of Hydrolysis and Initial Polycondensation Processes of Organoalkoxysilanes. I. Dimethyldiethoxysilane," J. Non-Cryst. Solids, 139, 25 (1992a).
86. Sugahara, Y., S. Okada, S. Sato, K. Kuroda, and C. Kato, "29Si-NMR Study of Hydrolysis and Initial Polycondensation Processes of Organoalkoxysilanes. II. Methyltriethoxysilanes," J. Non-Cryst. Solids, 167, 21 (1994).
87. Sugahara, Y., Y. Tanaka, S. Sato, K. Kuroda, and C. Kato, "Silicon-29 NMR Study on the Initial Stage of the Cohydrolysis of Tetraethoxysilane and Methyltriethoxysilane," Mater. Res. Soc. Symp. Proc., 271, 231 (1992b).
88. Tang, A., R. Xu, S. Li, and Y. An, "Characterisation of Polymeric Reaction in Silicic Acid Solution: Intramolecular Cyclization," J. Mater. Chem., 3, 893 (1993).
89. Vainrub, A., F. Devreux, J. P. Boilot, F. Chaput, and M. Sarkar, "Sol-Gel Polymerization in Alkoxysilanes: Si NMR Study and Simulation of Chemical Kinetics," Mater. Sei. Eng. B., 37, 197 (1996).
90. Voronkov, M. G., "Energy of the Si-O Bond and Ring Strain in Permethylcyclosiloxanes," Russ. J. Gen. Chem., 66, 165 (1996).
91. Wells, P. R., Linear Free Energy Relationship, Academic Press, London (1968).
92. Wilcock, D. F., "Liquid Methylpolysiloxane Systems," J. Amer. Chem. Soc., 69, 477 (1947).
93. Wood, D. L., and E. M. Rabinovich, "Heat Evolution, Light Scattering, and Infrared Spectroscopy in the Formation of Silica Gels from Alkoxides," J. Non-Cryst. Solids, 107, 199(1989).
94. Zhang, Z., Y. Tanigami, and R. Terai, "Preparation of Transparent Methyl-Modified Silica Gel," J. Non-Ciyst. Solids, 189, 212 (1995).