Year 2024,
Volume: 11 Issue: 3, 1211 - 1226, 30.08.2024
Seçil Sevim Ünlütürk
,
Necati Güdümcüoğlu
References
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- 3. Yi C, Rostron P, Vahdati N, Gunister E, Alfantazi A. Curing kinetics and mechanical properties of epoxy based coatings: The influence of added solvent. Progress in Organic Coatings. 2018;124:165-74. Available from:
<URL>.
- 4. Liu S, Li X, Ge M, Du X, Zou M. Curing Kinetics of Methylene Diphenyl Diisocyanate–Based Polyurethane Elastomers. Polymers. 2022;14(17):3525. Available from:
<URL>.
- 5. Manu SK, Sekkar V, Scariah KJ, Varghese TL, Mathew S. Kinetics of glycidyl azide polymer-based urethane network formation. Journal of Applied Polymer Science. 2008;110(2):908-14. Available from: <URL>.
- 6. Shundo A, Yamamoto S, Tanaka K. Network Formation and Physical Properties of Epoxy Resins for Future Practical Applications. JACS Au. 2022;2(7):1522-42. Available from: <URL>.
- 7. Balakrishnan R, Nallaperumal AM, Manu SKP, Varghese LA, Sekkar V. DSC assisted kinetic analysis on the urethane network formation between castor oil based ester polyol and poly(methylene di phenyl isocyanate) (pMDI). International Journal of Polymer Analysis and Characterization. 2022;27(2):132-46. Available from:
<URL>.
- 8. Balakrishnan R, Soumyamol PB, Vijayalakshmi KP, Alen Varghese L, Rajeev R, Manu SK, et al. Kinetic analysis of urethane formation between castor oil-based ester polyol and 4,4’-diphenyl methane diisocyanate. Indian Chemical Engineer. 2021;63(5):491-500. Available from: <URL>.
9. Hui M, Yu-Cun L, Tao C, Tuo-Ping H, Jia-Hu G, Yan- Wu Y, et al. Kinetic studies on the cure reaction of hydroxyl- terminated polybutadiene based polyurethane with variable catalysts by differential scanning calorimetry. e-Polymers. 2017;17(1):89-94. Available from: <URL>.
- 10. Schuster F, Ngako Ngamgoue F, Goetz T, Hirth T, Weber A, Bach M. Investigations of a catalyst system regarding the foamability of polyurethanes for reactive inkjet printing. Journal of Materials Chemistry C. 2017;5(27):6738-44. Available from: <URL>.
- 11. Kaushik A, Singh P. Kinetic Study of Polyurethane Reaction between Castor Oil/TMP Polyol and Diphenyl Methane Diisocyanate in Bulk. International Journal of Polymeric Materials and Polymeric Biomaterials. 2006;55(8):549-61. Available from: <URL>.
- 12. Vyazovkin S, Burnham AK, Criado JM, Pérez- Maqueda LA, Popescu C, Sbirrazzuoli N. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochimica Acta. 2011;520(1):1-19. Available from: <URL>.
- 13. Keskin S, Özkar S. Kinetics of polyurethane formation between glycidyl azide polymer and a triisocyanate. Journal of Applied Polymer Science. 2001;81(4):918-23. Available from: <URL>.
- 14. Kilivnik YN, Lipatova TE. The kinetics of formation of a crosslinked polyurethane in the presence of magnesium ions. Polymer Science USSR. 1976;18(12):3017-23. Available from: <URL>.
- 15. Stanko M, Stommel M. Kinetic Prediction of Fast Curing Polyurethane Resins by Model-Free Isoconversional Methods. Polymers. 2018;10(7):698. Available from:
<URL>.
- 16. Cui H-W, Suganuma K, Uchida H. Using the Ozawa method to study the thermally initiated curing kinetics of vinyl ester resin. RSC Advances. 2015;5(4):2677-83. Available from: <URL>.
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- 19. Shen Y, Tan J, Fernandes L, Qu Z, Li Y. Dynamic Mechanical Analysis on Delaminated Flax Fiber Reinforced Composites. Materials. 2019;12(16):2559. Available from:
<URL>.
- 20. Bertotto MM, Gastón A, Rodríguez Batiller MJ, Calello P. Comparison of mathematical models to predict glass transition temperature of rice (cultivar IRGA 424) measured by dynamic mechanical analysis. Food Sci Nutr. 2018;6(8):2199-209. Available from: <URL>.
- 21. Dias RCM, Góes AM, Serakides R, Ayres E, Oréfice RL. Porous biodegradable polyurethane nanocomposites: preparation, characterization, and biocompatibility tests. Materials Research. 2010;13. Available from: <URL>.
- 22. Zhang B, Wang B, Zhong Y, Wang S, Li X, Wang L. Experimental Study on Reducing the Heat of Curing Reaction of Polyurethane Polymer Grouting Material. Advances in Polymer Technology. 2021;2021:9954498. Available from: <URL>.
- 23. Remya Balakrishnan LAV, K Manu. Cure kinetics and thermodynamics of polyurethane network formation based on castor oil based polyester polyol and 4,4’-diphenyl methane diisocyanate. Indian Journal of Chemical Technology. 2021;28(3):7. Available from: <URL>.
- 24. Tziamtzi CK, Chrissafis K. Optimization of a commercial epoxy curing cycle via DSC data kinetics modelling and TTT plot construction. Polymer. 2021;230:124091. Available from: <URL>.
- 25. Hong JU, Lee TH, Oh D, Paik H-j, Noh SM. Scratch- healable automotive clearcoats based on disulfide polyacrylate urethane networks. Progress in Organic Coatings. 2021;161:106472. Available from: <URL>.
- 26. Sáenz-Pérez M, Lizundia E, Laza JM, García- Barrasa J, Vilas JL, León LM. Methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI) based polyurethanes: thermal, shape-memory and mechanical behavior. RSC Advances. 2016;6(73):69094-102. Available from: <URL>.
- 27. Cuevas JM, Cobos R, Germán L, Sierra B, Laza JM, Vilas-Vilela JL. Enhanced mar/scratch resistance in automotive clear coatings by modifying crosslinked polyurethane network with branched flexible oligomers. Progress in Organic Coatings. 2022;163:106668. Available from: <URL>.
- 28. Lee H-T, Lin L-H. Waterborne Polyurethane/Clay
Nanocomposites: Novel Effects of the Clay and Its Interlayer Ions on the Morphology and Physical and Electrical Properties. Macromolecules. 2006;39(18):6133-
41. Available from: <URL>.
- 29. Shi Y, Zhan X, Luo Z, Zhang Q, Chen F. Quantitative IR characterization of urea groups in waterborne polyurethanes. Journal of Polymer Science Part A: Polymer Chemistry. 2008;46(7):2433-44. Available from: <URL>.
- 30. Yin H, Sun DW, Li B, Liu YT, Ran QP, Liu JP. DSC and curing kinetics study of epoxy grouting diluted with furfural -acetone slurry. IOP Conference Series: Materials Science and Engineering. 2016;137(1):012001. Available from: <URL>.
- 31. Ma H, Zhang X, Ju F, Tsai S-B. A Study on Curing Kinetics of Nano-Phase Modified Epoxy Resin. Scientific Reports. 2018;8(1):3045. Available from: <URL>.
Curing Kinetic Analysis and Isothermal Prediction of DBTL Catalyzed Polyurethane Reaction by Differential Scanning Calorimetry
Year 2024,
Volume: 11 Issue: 3, 1211 - 1226, 30.08.2024
Seçil Sevim Ünlütürk
,
Necati Güdümcüoğlu
Abstract
Kinetic analysis is generally carried out to clarify the reaction mechanism with kinetic parameters and to predict the kinetic properties of materials under different reaction parameters. The kinetics of the polyurethane polymerisation reaction between acrylic polyol and isocyanate was investigated by Differential Scanning Calorimetry (DSC) in terms of catalyst amounts and sampling times. Single and multiple heating analyses were used to obtain DSC curves for each sample. The simple kinetic model and Multilinear Regression Fit (MRF) were used to calculate the kinetic parameters and simulate the isotherm prediction curves. The kinetic calculations showed that the glass transition temperatures (up to 44 oC) and activation energy (Ea) values increased with the degree of conversion for all cases. The reduction in the rate constant for partially cured samples was greater than the initial sampling time of the same sample. This observation indicates that the diffusion-controlled reaction dominates and Ea increases due to the highly cross-linked and dense medium in partially cured samples. Isothermal prediction curves provide an understanding of different curing conditions at different reaction temperatures and times. Prediction curves show slower conversion even for final samples, confirming that final samples may remain uncured. Applying the results of this study, especially for real-world applications, where fully cured samples are required, additional annealing procedures can be easily established.
Ethical Statement
There is no conflict of interest in this study.
Thanks
The authors acknowledge to Physical Chemistry Laboratory and Automotive Coatings of Kansai Altan Boya Sanayi for their support.
References
- 1. Groenewolt M. Polyurethane coatings: a perfect product class for the design of modern automotive clearcoats. Polymer International. 2019;68(5):843-7. Available from: <URL>.
- 2. Li K, Gan C, Zhang W, Li C, Li G. Validity of isothermal kinetic prediction by advanced isoconversional method. Chemical Physics. 2023;567:111801. Available from: <URL>.
- 3. Yi C, Rostron P, Vahdati N, Gunister E, Alfantazi A. Curing kinetics and mechanical properties of epoxy based coatings: The influence of added solvent. Progress in Organic Coatings. 2018;124:165-74. Available from:
<URL>.
- 4. Liu S, Li X, Ge M, Du X, Zou M. Curing Kinetics of Methylene Diphenyl Diisocyanate–Based Polyurethane Elastomers. Polymers. 2022;14(17):3525. Available from:
<URL>.
- 5. Manu SK, Sekkar V, Scariah KJ, Varghese TL, Mathew S. Kinetics of glycidyl azide polymer-based urethane network formation. Journal of Applied Polymer Science. 2008;110(2):908-14. Available from: <URL>.
- 6. Shundo A, Yamamoto S, Tanaka K. Network Formation and Physical Properties of Epoxy Resins for Future Practical Applications. JACS Au. 2022;2(7):1522-42. Available from: <URL>.
- 7. Balakrishnan R, Nallaperumal AM, Manu SKP, Varghese LA, Sekkar V. DSC assisted kinetic analysis on the urethane network formation between castor oil based ester polyol and poly(methylene di phenyl isocyanate) (pMDI). International Journal of Polymer Analysis and Characterization. 2022;27(2):132-46. Available from:
<URL>.
- 8. Balakrishnan R, Soumyamol PB, Vijayalakshmi KP, Alen Varghese L, Rajeev R, Manu SK, et al. Kinetic analysis of urethane formation between castor oil-based ester polyol and 4,4’-diphenyl methane diisocyanate. Indian Chemical Engineer. 2021;63(5):491-500. Available from: <URL>.
9. Hui M, Yu-Cun L, Tao C, Tuo-Ping H, Jia-Hu G, Yan- Wu Y, et al. Kinetic studies on the cure reaction of hydroxyl- terminated polybutadiene based polyurethane with variable catalysts by differential scanning calorimetry. e-Polymers. 2017;17(1):89-94. Available from: <URL>.
- 10. Schuster F, Ngako Ngamgoue F, Goetz T, Hirth T, Weber A, Bach M. Investigations of a catalyst system regarding the foamability of polyurethanes for reactive inkjet printing. Journal of Materials Chemistry C. 2017;5(27):6738-44. Available from: <URL>.
- 11. Kaushik A, Singh P. Kinetic Study of Polyurethane Reaction between Castor Oil/TMP Polyol and Diphenyl Methane Diisocyanate in Bulk. International Journal of Polymeric Materials and Polymeric Biomaterials. 2006;55(8):549-61. Available from: <URL>.
- 12. Vyazovkin S, Burnham AK, Criado JM, Pérez- Maqueda LA, Popescu C, Sbirrazzuoli N. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochimica Acta. 2011;520(1):1-19. Available from: <URL>.
- 13. Keskin S, Özkar S. Kinetics of polyurethane formation between glycidyl azide polymer and a triisocyanate. Journal of Applied Polymer Science. 2001;81(4):918-23. Available from: <URL>.
- 14. Kilivnik YN, Lipatova TE. The kinetics of formation of a crosslinked polyurethane in the presence of magnesium ions. Polymer Science USSR. 1976;18(12):3017-23. Available from: <URL>.
- 15. Stanko M, Stommel M. Kinetic Prediction of Fast Curing Polyurethane Resins by Model-Free Isoconversional Methods. Polymers. 2018;10(7):698. Available from:
<URL>.
- 16. Cui H-W, Suganuma K, Uchida H. Using the Ozawa method to study the thermally initiated curing kinetics of vinyl ester resin. RSC Advances. 2015;5(4):2677-83. Available from: <URL>.
- 17. Vyazovkin S. Kissinger Method in Kinetics of Materials: Things to Beware and Be Aware of. Molecules. 2020;25(12). Available from: <URL>.
- 18. Shamsi R, Mir Mohamad Sadeghi G, Asghari GH. Dynamic mechanical analysis of polyurethanes and carbon nanotube based composites obtained from PET waste. Polymer Composites. 2018;39(S2):E754-E64. Available from: <URL>.
- 19. Shen Y, Tan J, Fernandes L, Qu Z, Li Y. Dynamic Mechanical Analysis on Delaminated Flax Fiber Reinforced Composites. Materials. 2019;12(16):2559. Available from:
<URL>.
- 20. Bertotto MM, Gastón A, Rodríguez Batiller MJ, Calello P. Comparison of mathematical models to predict glass transition temperature of rice (cultivar IRGA 424) measured by dynamic mechanical analysis. Food Sci Nutr. 2018;6(8):2199-209. Available from: <URL>.
- 21. Dias RCM, Góes AM, Serakides R, Ayres E, Oréfice RL. Porous biodegradable polyurethane nanocomposites: preparation, characterization, and biocompatibility tests. Materials Research. 2010;13. Available from: <URL>.
- 22. Zhang B, Wang B, Zhong Y, Wang S, Li X, Wang L. Experimental Study on Reducing the Heat of Curing Reaction of Polyurethane Polymer Grouting Material. Advances in Polymer Technology. 2021;2021:9954498. Available from: <URL>.
- 23. Remya Balakrishnan LAV, K Manu. Cure kinetics and thermodynamics of polyurethane network formation based on castor oil based polyester polyol and 4,4’-diphenyl methane diisocyanate. Indian Journal of Chemical Technology. 2021;28(3):7. Available from: <URL>.
- 24. Tziamtzi CK, Chrissafis K. Optimization of a commercial epoxy curing cycle via DSC data kinetics modelling and TTT plot construction. Polymer. 2021;230:124091. Available from: <URL>.
- 25. Hong JU, Lee TH, Oh D, Paik H-j, Noh SM. Scratch- healable automotive clearcoats based on disulfide polyacrylate urethane networks. Progress in Organic Coatings. 2021;161:106472. Available from: <URL>.
- 26. Sáenz-Pérez M, Lizundia E, Laza JM, García- Barrasa J, Vilas JL, León LM. Methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI) based polyurethanes: thermal, shape-memory and mechanical behavior. RSC Advances. 2016;6(73):69094-102. Available from: <URL>.
- 27. Cuevas JM, Cobos R, Germán L, Sierra B, Laza JM, Vilas-Vilela JL. Enhanced mar/scratch resistance in automotive clear coatings by modifying crosslinked polyurethane network with branched flexible oligomers. Progress in Organic Coatings. 2022;163:106668. Available from: <URL>.
- 28. Lee H-T, Lin L-H. Waterborne Polyurethane/Clay
Nanocomposites: Novel Effects of the Clay and Its Interlayer Ions on the Morphology and Physical and Electrical Properties. Macromolecules. 2006;39(18):6133-
41. Available from: <URL>.
- 29. Shi Y, Zhan X, Luo Z, Zhang Q, Chen F. Quantitative IR characterization of urea groups in waterborne polyurethanes. Journal of Polymer Science Part A: Polymer Chemistry. 2008;46(7):2433-44. Available from: <URL>.
- 30. Yin H, Sun DW, Li B, Liu YT, Ran QP, Liu JP. DSC and curing kinetics study of epoxy grouting diluted with furfural -acetone slurry. IOP Conference Series: Materials Science and Engineering. 2016;137(1):012001. Available from: <URL>.
- 31. Ma H, Zhang X, Ju F, Tsai S-B. A Study on Curing Kinetics of Nano-Phase Modified Epoxy Resin. Scientific Reports. 2018;8(1):3045. Available from: <URL>.