A REVIEW OF MEASURING THE GELATION TIME IN UNSATURATED POLYESTER RESINS
Keywords:
unsaturated polyester resin, gel time, catalyst, accelerator, inhibitor, filler
Abstract
Unsaturated polyester resins (UPRs) are commonly used as matrix resins for fiber-reinforced composites. During processing, the resins undergo a molecular cross-linking process called curing, during which they change irreversibly from viscous liquids to rigid and highly cross-linked polymer solids. The gelation time is critical for the success of a resin system, but it is difficult to measure accurately. It depends on several parameters. In this study, the parameters investigated are the effect of choice and their relative proportions. Parameters such as catalyst, accelerators, inhibitor, and fillers were examined. Various combinations of catalyst, accelerator, inhibitor, temperature and filler were analyzed to investigate the effect on the gel time of the unsaturated polyester resins. Then, this review assembles the scientific data on the gelation of unsaturated polyester resins to help readers better understand this process. Students, researchers, technologists, engineers, and chemists involved in the technology of synthesizing these monomers and polymers will benefit from this material.
References
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[3] A. D2471-99, “Standard Test Method for Gel Time and Peak Exothermic Temperature of Reacting,” ASTM International, vol. 08, pp. 1–3, 2000.
[4] M. Farsane, L. Soufia, A. Anouar, S. Chah, S. Dagdag, and M. Bouzziri, “Experimental evaluation of the curing of unsaturated polyester resin at various amounts of methyl ethyl ketone peroxide, cobalt octoate and porcelain powder,” Revista de Chimie, vol. 71, no. 10, pp. 58–66, 2020.
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[9] W. D. Cook, M. Lau, M. Mehrabi, K. Dean, and Marcus Zipper, “Control of gel time and exotherm behaviour during cure of unsaturated polyester resins,” Polymer International, vol. 50, no. 1, pp. 129–134, 2001.
[10] C. Walling, “Gel Formation in Addition Polymerization,” Journal of the American Chemical Society, vol. 67, no. 3, pp. 441–447, 1945.
[11] J. Simitzis, A. Stamboulis, D. Tsoros, and N. Martakis, “Kinetics of Curing of Unsaturated Polyesters in the Presence of Organic and Inorganic Fillers,” Polymer International, vol. 43, no. 4, pp. 380–384, 1997.
[12] S. D. Gordin, A. M. Eslami, and H. L. Price, “Gel time and temperature for two thermosetting resins,” ASEE Annual Conference Proceedings, pp. 6077–6086, 2004.
[13] A. A. Shimkin, “Methods for the determination of the gel time of polymer resins and prepregs,” Russian Journal of General Chemistry, vol. 86, no. 6, pp. 1488–1493, 2016.
[14] “Gel Time Determination of Epoxy resin system.pdf.” .
[15] L. Núñez-Regueira, C. A. Gracia-Fernández, and S. Gómez-Barreiro, “Use of rheology, dielectric analysis and differential scanning calorimetry for gel time determination of a thermoset,” Polymer, vol. 46, no. 16, pp. 5979–5985, 2005.
[16] No 主観的健康感を中心とした在宅高齢者における 健康関連指標に関する共分散構造分析Title. .
[17] R. J. Varley, J. H. Hodgkin, D. G. Hawthorne, and G. P. Simon, “Toughening of a trifunctional epoxy system. II. Thermal characterization of epoxy/amine cure,” Journal of Applied Polymer Science, vol. 60, no. 12, pp. 2251–2263, 1996.
[18] J. Gao, L. Li, Y. Deng, Z. Gao, C. Xu, and M. Zhang, “Study of gelation using Differential Scanning Calorimetry (DSC),” Journal of Thermal Analysis, vol. 49, no. 1, pp. 303–310, 1997.
[19] N. C. Restrepo-Zapata, T. A. Osswald, and J. P. Hernández-Ortiz, “Method for time-temperature-transformation diagrams using DSC data: Linseed aliphatic epoxy resin,” Journal of Applied Polymer Science, vol. 131, no. 15, pp. 1–13, 2014.
[20] M. A. Acitelli, R. B. Prime, and E. Sacher, “Kinetics of epoxy cure: (1) The system bisphenol-A diglycidyl ether/m-phenylene diamine,” Polymer, vol. 12, no. 5, pp. 335–343, 1971.
[21] F. Lionetto and A. Maffezzoli, “Monitoring the cure state of thermosetting resins by ultrasound,” Materials, vol. 6, no. 9, pp. 3783–3804, 2013.
[22] X. Ramis and J. M. Salla, “Time-temperature transformation (TTT) cure diagram of an unsaturated polyester resin,” Journal of Polymer Science, Part B: Polymer Physics, vol. 35, no. 2, pp. 371–388, 1997.
[23] P. Beaunez, G. Helary, and G. Sauvet, “Role of N,N-dimethyl-para-toluidine and Saccharin in the Radical Polymerization,” Journal of Polymer Science Part A: Polymer Chemistry, vol. 32, no. 8, pp. 1471–1480, 1994.
[24] G. L. Batch and C. W. Macosko, “Kinetic model for crosslinking free radical polymerization including diffusion limitations,” Journal of Applied Polymer Science, vol. 44, no. 10, pp. 1711–1729, 1992.
[25] X. RAMIS, “Effect of the Initiator Content and Temperature on the Curing of an Unsaturated Polyester Resin,” Polymer Science Physics, vol. 37, no. 18, pp. 751–768, 1999.
[26] W. D. Cook, G. P. Simon, P. J. Burchill, M. Lau, and T. J. Fitch, “Curing kinetics and thermal properties of vinyl ester resins,” Journal of Applied Polymer Science, vol. 64, no. 4, pp. 769–781, 1997.
[27] M. Vafayan, M. H. Beheshty, and H. Nasiri, “A kinetic model for the low temperature curing of an unsaturated polyester resin with single and dual initiators,” Polymers and Polymer Composites, vol. 15, no. 3, pp. 183–190, 2007.
[28] E. L. Rodriguez, “The effect of free radical initiators and fillers on the cure of unsaturated polyester resins,” Polymer Engineering & Science, vol. 31, no. 14, pp. 1022–1028, 1991.
[29] J. L. Vilas, J. M. Laza, M. T. Garay, M. Rodríguez, and L. M. León, “Unsaturated polyester resins cure: kinetic, rheologic, and mechanical dynamical analysis. II. The glass transition in the mechanical dynamical spectrum of polyester networks,” Journal of Polymer Science, Part B: Polymer Physics, vol. 39, no. 1, pp. 146–152, 2001.
[30] L. Li, X. Cao, and L. J. Lee, “Effect of dual-initiator on low temperature curing of unsaturated polyester resins,” Polymer, vol. 45, no. 19, pp. 6601–6612, 2004.
[31] X. Cao and L. J. Lee, “Control of volume shrinkage and residual styrene of unsaturated polyester resins cured at low temperatures. II. Effect of comonomer,” Polymer, vol. 44, no. 5, pp. 1507–1516, 2003.
[32] J. L. Martín, “Kinetic analysis of an asymmetrical DSC peak in the curing of an unsaturated polyester resin catalysed with MEKP and cobalt octoate,” Polymer, vol. 40, no. 12, pp. 3451–3462, 1999.
[33] Y. ‐S Yang and L. Suspene, “Curing of unsaturated polyester resins: Viscosity studies and simulations in pre‐gel state,” Polymer Engineering & Science, vol. 31, no. 5, pp. 321–332, 1991.
[34] C. Andronescu, P. O. Stãnescu, S. A. Garea, and H. Iovu, “Influence of curing protocol of benzoxazine monomer based on aromatic diamines against the degradation behaviour of the resulted polybenzoxazines,” Materiale Plastice, vol. 50, no. 2, pp. 146–151, 2013.
[35] X. Ramis and J. M. Salla, “Effect of the inhibitor on the curing of an unsaturated polyester resin,” Polymer, vol. 36, no. 18, pp. 3511–3521, 1995.
[36] Y. J. Huang and J. S. Leu, “Curing of unsaturated polyester resins. Effects of temperature and initiator: 1. Low temperature reactions,” Polymer, vol. 34, no. 2, pp. 295–304, 1993.
[37] A. J. Rojas, J. Borrajo, and R. J. J. Williams, “The curing of unsaturated polyester resins in adiabatic reactors and heated molds,” Polymer Engineering & Science, vol. 21, no. 17, pp. 1122–1127, 1981.
[38] J. Ampudia, E. Larrauri, E. M. Gil, M. Rodríguez, and L. M. León, “Thermal scanning rheometric analysis of curing kinetic of an epoxy resin. I. An anhydride as curing agent,” Journal of Applied Polymer Science, vol. 71, no. 8, pp. 1239–1245, 2002.
[39] S. Y. Kim, D. G. Choi, and S. M. Yang, “Rheological Analysis of the Gelation Behavior of Tetraethylorthosilane/Vinyltriethoxysilane Hybrid Solutions,” Korean Journal of Chemical Engineering, vol. 19, no. 1, pp. 190–196, 2002.
[40] C. N. Cascaval and A. Mija, “Liquid crystalline epoxy thermosets,” Materiale Plastice, vol. 45, no. 4, pp. 339–344, 2008.
[41] F. Mustata, “Synthesis and characterization of novel methylenedianiline/tertbutylphenol formaldehyde resins as hardeners for epoxy resins,” Materiale Plastice, vol. 47, no. 2, pp. 146–152, 2010.
[42] K. De La Caba, P. Guerrero, A. Eceiza, and I. Mondragon, “Kinetic and rheological studies of two unsaturated polyester resins cured at different temperatures,” European Polymer Journal, vol. 33, no. 1, pp. 19–23, 1997.
[43] C. P. Hsu and L. J. Lee, “Free-radical crosslinking copolymerization of styrene/unsaturated polyester resins: 3. Kinetics-gelation mechanism,” Polymer, vol. 34, no. 21, pp. 4516–4523, 1993.
[44] C. P. Hsu and L. J. Lee, “Free-radical crosslinking copolymerization of styrene/unsaturated polyester resins: 1. Phase separation and microgel formation,” Polymer, vol. 34, no. 21, pp. 4496–4505, 1993.
[45] Y. Nakagawa, S. Banno, and K. Matsuyama, “Control in curing of unsaturated polyester resin,” Advanced Composite Materials, vol. 2, no. 4, pp. 319–328, 1992.
[46] R. G. Weatherhead, “Catalysts, Accelerators and Inhibitors for Unsaturated Polyester Resins,” FRP Technology, pp. 204–239, 1980.
[47] H. Kubota, “Curing of highly reactive polyester resin under pressure: Kinetic studies by differential scanning calorimetry,” Journal of Applied Polymer Science, vol. 19, no. 8, pp. 2279–2297, 1975.
[48] J. C. Lucas, J. Borrajo, and R. J. J. Williams, “Cure of unsaturated polyester resins: 2. Influence of low-profile additives and fillers on the polymerization reaction, mechanical properties and surface rugosities,” Polymer, vol. 34, no. 9, pp. 1886–1890, 1993.
[2] R. R. P. Kuppusamy and S. Neogi, “Influence of curing agents on gelation and exotherm behaviour of an unsaturated polyester resin,” Bulletin of Materials Science, vol. 36, no. 7, pp. 1217–1224, 2013.
[3] A. D2471-99, “Standard Test Method for Gel Time and Peak Exothermic Temperature of Reacting,” ASTM International, vol. 08, pp. 1–3, 2000.
[4] M. Farsane, L. Soufia, A. Anouar, S. Chah, S. Dagdag, and M. Bouzziri, “Experimental evaluation of the curing of unsaturated polyester resin at various amounts of methyl ethyl ketone peroxide, cobalt octoate and porcelain powder,” Revista de Chimie, vol. 71, no. 10, pp. 58–66, 2020.
[5] Y. S. Yang and L. J. Lee, “Polymerization of Polyurethane-Polyester Interpenetrating Polymer Network (IPN),” Macromolecules, vol. 20, no. 7, pp. 1490–1495, 1987.
[6] S. Y. Tawfik, J. N. Asaad, and M. W. Sabaa, “Effect of polyester backbone structure on the cured products properties,” Polymer Testing, vol. 22, no. 7, pp. 747–759, 2003.
[7] M. Farsane, A. Anouar, S. Chah, S. Dagdag, and M. Bouzziri, “Study of experimental investigations in the presence of ceramic waste powder,” Materiale Plastice, vol. 57, no. 4, pp. 1–12, 2021.
[8] J. M. Kenny, A. Maffezzoli, and L. Nicolais, “A model for the thermal and chemorheological behavior of thermoset processing: (II) Unsaturated polyester based composites,” Composites Science and Technology, vol. 38, no. 4, pp. 339–358, 1990.
[9] W. D. Cook, M. Lau, M. Mehrabi, K. Dean, and Marcus Zipper, “Control of gel time and exotherm behaviour during cure of unsaturated polyester resins,” Polymer International, vol. 50, no. 1, pp. 129–134, 2001.
[10] C. Walling, “Gel Formation in Addition Polymerization,” Journal of the American Chemical Society, vol. 67, no. 3, pp. 441–447, 1945.
[11] J. Simitzis, A. Stamboulis, D. Tsoros, and N. Martakis, “Kinetics of Curing of Unsaturated Polyesters in the Presence of Organic and Inorganic Fillers,” Polymer International, vol. 43, no. 4, pp. 380–384, 1997.
[12] S. D. Gordin, A. M. Eslami, and H. L. Price, “Gel time and temperature for two thermosetting resins,” ASEE Annual Conference Proceedings, pp. 6077–6086, 2004.
[13] A. A. Shimkin, “Methods for the determination of the gel time of polymer resins and prepregs,” Russian Journal of General Chemistry, vol. 86, no. 6, pp. 1488–1493, 2016.
[14] “Gel Time Determination of Epoxy resin system.pdf.” .
[15] L. Núñez-Regueira, C. A. Gracia-Fernández, and S. Gómez-Barreiro, “Use of rheology, dielectric analysis and differential scanning calorimetry for gel time determination of a thermoset,” Polymer, vol. 46, no. 16, pp. 5979–5985, 2005.
[16] No 主観的健康感を中心とした在宅高齢者における 健康関連指標に関する共分散構造分析Title. .
[17] R. J. Varley, J. H. Hodgkin, D. G. Hawthorne, and G. P. Simon, “Toughening of a trifunctional epoxy system. II. Thermal characterization of epoxy/amine cure,” Journal of Applied Polymer Science, vol. 60, no. 12, pp. 2251–2263, 1996.
[18] J. Gao, L. Li, Y. Deng, Z. Gao, C. Xu, and M. Zhang, “Study of gelation using Differential Scanning Calorimetry (DSC),” Journal of Thermal Analysis, vol. 49, no. 1, pp. 303–310, 1997.
[19] N. C. Restrepo-Zapata, T. A. Osswald, and J. P. Hernández-Ortiz, “Method for time-temperature-transformation diagrams using DSC data: Linseed aliphatic epoxy resin,” Journal of Applied Polymer Science, vol. 131, no. 15, pp. 1–13, 2014.
[20] M. A. Acitelli, R. B. Prime, and E. Sacher, “Kinetics of epoxy cure: (1) The system bisphenol-A diglycidyl ether/m-phenylene diamine,” Polymer, vol. 12, no. 5, pp. 335–343, 1971.
[21] F. Lionetto and A. Maffezzoli, “Monitoring the cure state of thermosetting resins by ultrasound,” Materials, vol. 6, no. 9, pp. 3783–3804, 2013.
[22] X. Ramis and J. M. Salla, “Time-temperature transformation (TTT) cure diagram of an unsaturated polyester resin,” Journal of Polymer Science, Part B: Polymer Physics, vol. 35, no. 2, pp. 371–388, 1997.
[23] P. Beaunez, G. Helary, and G. Sauvet, “Role of N,N-dimethyl-para-toluidine and Saccharin in the Radical Polymerization,” Journal of Polymer Science Part A: Polymer Chemistry, vol. 32, no. 8, pp. 1471–1480, 1994.
[24] G. L. Batch and C. W. Macosko, “Kinetic model for crosslinking free radical polymerization including diffusion limitations,” Journal of Applied Polymer Science, vol. 44, no. 10, pp. 1711–1729, 1992.
[25] X. RAMIS, “Effect of the Initiator Content and Temperature on the Curing of an Unsaturated Polyester Resin,” Polymer Science Physics, vol. 37, no. 18, pp. 751–768, 1999.
[26] W. D. Cook, G. P. Simon, P. J. Burchill, M. Lau, and T. J. Fitch, “Curing kinetics and thermal properties of vinyl ester resins,” Journal of Applied Polymer Science, vol. 64, no. 4, pp. 769–781, 1997.
[27] M. Vafayan, M. H. Beheshty, and H. Nasiri, “A kinetic model for the low temperature curing of an unsaturated polyester resin with single and dual initiators,” Polymers and Polymer Composites, vol. 15, no. 3, pp. 183–190, 2007.
[28] E. L. Rodriguez, “The effect of free radical initiators and fillers on the cure of unsaturated polyester resins,” Polymer Engineering & Science, vol. 31, no. 14, pp. 1022–1028, 1991.
[29] J. L. Vilas, J. M. Laza, M. T. Garay, M. Rodríguez, and L. M. León, “Unsaturated polyester resins cure: kinetic, rheologic, and mechanical dynamical analysis. II. The glass transition in the mechanical dynamical spectrum of polyester networks,” Journal of Polymer Science, Part B: Polymer Physics, vol. 39, no. 1, pp. 146–152, 2001.
[30] L. Li, X. Cao, and L. J. Lee, “Effect of dual-initiator on low temperature curing of unsaturated polyester resins,” Polymer, vol. 45, no. 19, pp. 6601–6612, 2004.
[31] X. Cao and L. J. Lee, “Control of volume shrinkage and residual styrene of unsaturated polyester resins cured at low temperatures. II. Effect of comonomer,” Polymer, vol. 44, no. 5, pp. 1507–1516, 2003.
[32] J. L. Martín, “Kinetic analysis of an asymmetrical DSC peak in the curing of an unsaturated polyester resin catalysed with MEKP and cobalt octoate,” Polymer, vol. 40, no. 12, pp. 3451–3462, 1999.
[33] Y. ‐S Yang and L. Suspene, “Curing of unsaturated polyester resins: Viscosity studies and simulations in pre‐gel state,” Polymer Engineering & Science, vol. 31, no. 5, pp. 321–332, 1991.
[34] C. Andronescu, P. O. Stãnescu, S. A. Garea, and H. Iovu, “Influence of curing protocol of benzoxazine monomer based on aromatic diamines against the degradation behaviour of the resulted polybenzoxazines,” Materiale Plastice, vol. 50, no. 2, pp. 146–151, 2013.
[35] X. Ramis and J. M. Salla, “Effect of the inhibitor on the curing of an unsaturated polyester resin,” Polymer, vol. 36, no. 18, pp. 3511–3521, 1995.
[36] Y. J. Huang and J. S. Leu, “Curing of unsaturated polyester resins. Effects of temperature and initiator: 1. Low temperature reactions,” Polymer, vol. 34, no. 2, pp. 295–304, 1993.
[37] A. J. Rojas, J. Borrajo, and R. J. J. Williams, “The curing of unsaturated polyester resins in adiabatic reactors and heated molds,” Polymer Engineering & Science, vol. 21, no. 17, pp. 1122–1127, 1981.
[38] J. Ampudia, E. Larrauri, E. M. Gil, M. Rodríguez, and L. M. León, “Thermal scanning rheometric analysis of curing kinetic of an epoxy resin. I. An anhydride as curing agent,” Journal of Applied Polymer Science, vol. 71, no. 8, pp. 1239–1245, 2002.
[39] S. Y. Kim, D. G. Choi, and S. M. Yang, “Rheological Analysis of the Gelation Behavior of Tetraethylorthosilane/Vinyltriethoxysilane Hybrid Solutions,” Korean Journal of Chemical Engineering, vol. 19, no. 1, pp. 190–196, 2002.
[40] C. N. Cascaval and A. Mija, “Liquid crystalline epoxy thermosets,” Materiale Plastice, vol. 45, no. 4, pp. 339–344, 2008.
[41] F. Mustata, “Synthesis and characterization of novel methylenedianiline/tertbutylphenol formaldehyde resins as hardeners for epoxy resins,” Materiale Plastice, vol. 47, no. 2, pp. 146–152, 2010.
[42] K. De La Caba, P. Guerrero, A. Eceiza, and I. Mondragon, “Kinetic and rheological studies of two unsaturated polyester resins cured at different temperatures,” European Polymer Journal, vol. 33, no. 1, pp. 19–23, 1997.
[43] C. P. Hsu and L. J. Lee, “Free-radical crosslinking copolymerization of styrene/unsaturated polyester resins: 3. Kinetics-gelation mechanism,” Polymer, vol. 34, no. 21, pp. 4516–4523, 1993.
[44] C. P. Hsu and L. J. Lee, “Free-radical crosslinking copolymerization of styrene/unsaturated polyester resins: 1. Phase separation and microgel formation,” Polymer, vol. 34, no. 21, pp. 4496–4505, 1993.
[45] Y. Nakagawa, S. Banno, and K. Matsuyama, “Control in curing of unsaturated polyester resin,” Advanced Composite Materials, vol. 2, no. 4, pp. 319–328, 1992.
[46] R. G. Weatherhead, “Catalysts, Accelerators and Inhibitors for Unsaturated Polyester Resins,” FRP Technology, pp. 204–239, 1980.
[47] H. Kubota, “Curing of highly reactive polyester resin under pressure: Kinetic studies by differential scanning calorimetry,” Journal of Applied Polymer Science, vol. 19, no. 8, pp. 2279–2297, 1975.
[48] J. C. Lucas, J. Borrajo, and R. J. J. Williams, “Cure of unsaturated polyester resins: 2. Influence of low-profile additives and fillers on the polymerization reaction, mechanical properties and surface rugosities,” Polymer, vol. 34, no. 9, pp. 1886–1890, 1993.
Published
2022-06-07
How to Cite
1.
Farsane M, Lhasnaoui S, Anouar A, Dagdag S, Bouzziri M. A REVIEW OF MEASURING THE GELATION TIME IN UNSATURATED POLYESTER RESINS. MatTech [Internet]. 2022Jun.7 [cited 2025Apr.29];56(3):323–329. Available from: https://mater-tehnol.si/index.php/MatTech/article/view/337
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