In this study, the authors study by calorimetry the influence of hyperbranched polyester Boltron®H40 on the thermal curing and the photocuring of a diglycidyl ether of bisphenol epoxy resin (DGEBA) using ytterbium (III) trifluoromethanesulfonate and triarylsulfonium hexafluorantimonate as thermal and photo cationic initiators, respectively. In the dynamic thermal curing at different heating rates, the authors have seen a decelerating effect when H40 is added to DGEBA, the system with 10% of H40 being the slowest. An isoconversional method has been used to determine the apparent activation energy of the thermal curing. In the isothermal photocuring at low temperatures, the authors have also appreciated a decelerating effect on adding H40, obtaining a minimum conversion when the H40 proportion is 15%. However, at high temperatures, the photocuring process can be accelerated at the first part of this process. This behavior is a consequence of the temperature dependence of H40 solubility in DGEBA, the viscosity of the system, and the hydroxyl-induced chain-transfer reaction. The values found of the maximum glass transition temperature in the thermal curing and in the photocuring, show that H40 is not completely solubilized in the reacted system.
1. Sörensen K , Pettersson BO, Boogh L, Månson JAE. Dendritic polyester macromolecule in thermosetting resin matrix. PCT Pat./SE94/04440, 1994.
2. Mezzenga, R, Boogh, L, Månson, JAE 2001 A review of dendritic hyperbranched polymer as modifiers in epoxy composites. Compos Sci Technol 61:787–795 .
3. Zhang, Y, Zhang, D, Qin, C, Xu, J 2009 Physical and mechanical properties of dental nanocomposites composed of aliphatic epoxy resin and epoxidized aromatic hyperbranched polymers. Polym Compos 30:176–181 .
4. Riew CK , Siebert AR, Smith RW, Fernando M, Kinloch AJ. Toughened epoxy resins: preformed particles as tougheners for adhesives and matrices. In: Riew CK, Kinloch AJ, editors. Toughened plastics II novel approaches in science and engineering. Advances in chemical series, vol 252. Washington: American Chemical Society; 1996. p. 33–44.
5. Wu, SH 1985 Phase structure and adhesion in polymer blends: a criterion for rubber technology. Polymer 26:1855–1863 .
6. Pearson, RA, Yee, AF 1993 Toughening mechanisms in thermoplastic-modified epoxies: 1. Modification using poly(phenylene oxide). Polymer 34:3658–3670 .
7. Hedrick, JL, Yilgor, I, Jurek, M, Hedrick, JC, Wilkes, GL, McGrath, JE 1991 Chemical modification of matrix resin networks with engineering thermoplastics: 1. Synthesis, morphology, physical behaviour and toughening mechanisms of poly(arylene ether sulphone) modified epoxy networks. Polymer 32:2020–2032 .
8. Wilkinson, SP, Ward, TC, McGrath, JE 1993 Effect of thermoplastic modifier variables on toughening a bismaleimide matrix resin for high-performance composite materials. Polymer 34:870–884 .
9. Kunz, SC, Sayre, JA, Assink, RA 1982 Morphology and toughness characterization of epoxy resins modified with amine and carboxyl terminated rubbers. Polymer 23:1897–1906 .
10. Mezzenga, R, Plummer, CJG, Boogh, L, Månson, JAE 2001 Morphology build-up in dendritic hyperbranched polymer modified epoxy resins: modelling and characterization. Polymer 42:305–317 .
11. Kinloch, AJ, Shaw, SJ, Tod, DA, Hunston, DL 1983 Deformation and fracture behaviour of a rubber-toughened epoxy: 1. Microstructure and fracture studies. Polymer 24:1341–1354 .
12. Ho, T-H, Wang, C-S 1993 Toughening of epoxy resins by modification with dispersed acrylate rubber for electronic packaging. J Appl Polym Sci 50:477–483 .
13. Guo, QP, Habrard, A, Park, Y, Halley, PJ, Simon, GP 2006 Phase separation, porous structure, and cure kinetics in aliphatic epoxy resin containing hyperbranched polyester. J Polym Sci B 44:889–899 .
14. Ratna, D, Varley, R, Simon, GP 2003 Toughening of trifunctional epoxy using an epoxy-functionalized hyperbranched polymer. J Appl Polym Sci 89:2339–2345 .
15. He, S, Shi, K, Bai, J, Zhang, Z, Li, L, Du, Z, Zhang, B 2001 Studies on the properties of epoxy resins modified with chain-extended ureas. Polymer 42:9641–9647 .
16. Evans, D, Canfer, SJ 2000 Radiation stable, low viscosity impregnating resin systems for cryogenic applications. Adv Cryog Eng 46:361–368.
17. Ueki, T, Nishijima, S, Izumi, Y 2005 Designing of epoxy resin systems for cryogenic use. Cryogenics 45:141–148 .
18. Nishijima, S, Honda, Y, Okada, T 1995 Application of the positron annihilation method for evaluation of organic materials for cryogenic use. Cryogenics 35:779–781 .
19. Yang, J-P, Chen, Z-K, Yang, G, Fu, S-Y, Ye, L 2008 Simultaneous improvements in the cryogenic tensile strength, ductility and impact strength of epoxy resins by a hyperbranched polymer. Polymer 49:3168–3175 .
20. Sangermano, M, Malucelli, G, Bongiovanni, R, Priola, A, Harden, A, Rehnberg, N 2003 Hyperbranched polymers in cationic photopolymerization of epoxy systems. Polym Eng Sci 43:1460–1465 .
21. Esposito Corcione, C, Malucelli, G, Frigione, M, Maffezzoli, A 2009 UV-curable epoxy systems containing hyperbranched polymers: kinetics investigation by photo-DSC and real-time FT–IR experiments. Polym Test 28:157–164 .
22. Fernández-Francos, X, Salla, JM, Cadenato, A, Morancho, JM, Serra, A, Mantecón, A, Ramis, X 2009 A new strategy for controlling shrinkage of DGEBA resins cured by cationic copolymerization with hydroxyl-terminated hyperbranched polymers and ytterbium triflate as an initiator. J Appl Polym Sci 111:2822–2829 .
23. Sangermano, M, Malucelli, G, Bongiovanni, R, Priola, A, Harden, A 2005 Investigation on the effect of the presence of hyperbranched polymers on thermal and mechanical properties of an epoxy UV-cured system. Polym Int 54:917–921 .
24. Morancho, JM, Cadenato, A, Ramis, X, Fernández-Francos, X, Salla, JM 2010 Thermal curing and photocuring of an epoxy resin modified with a hyperbranched polymer. Thermochim Acta 510:1–8 .
25. Doyle, CD 1965 Series approximations to the equation of thermogravimetric data. Nature 207:290–291 .
26. Ozawa, T 1965 New method of analyzing thermogravimetric data. Bull Chem Soc Jpn 38:1881–1886 .
27. Tryson, GR, Shultz, AR 1979 A calorimetric study of acrylate photopolymerization. J Polym Sci 17:2059–2075.
28. Morancho, JM, Cadenato, A, Fernández-Francos, X, Salla, JM, Ramis, X 2008 Isothermal kinetics of photopolymerization and thermal polymerization of bis-GMA/TEGDMA resins. J Therm Anal Calorim 92:513–522 .
29. Lecamp, L, Youssef, B, Bunel, C, Labaudy, P 1999 Photoinitiated polymerization of a dimethacrylate oligomer: 2. Kinetic studies. Polymer 40:1403–1409 .
30. Watts, DC 2005 Reaction kinetics and mechanics in photo-polymerised networks. Dent Mater 21:27–35 .
31. Cook, WD 1992 Thermal aspects of the kinetics of dimethacrylate photopolymerization. Polymer 33:2152–2161 .
32. Fox, TG 1956 Influence of diluent and of copolymer composition on the glass temperature of a polymer system. Bull Am Phys Soc 1:123.
33. Scott, TT, Cook, WD, Forsythe, JS 2002 Photo-DSC cure kinetics of vinyl ester resins. I. Influence of temperature. Polymer 43:5839–5845 .
34. Fernández-Francos, X, Salla, JM, Cadenato, A, Morancho, JM, Mantecón, A, Serra, A, Ramis, X 2007 Influence of the initiating mechanism on the cationic photopolymerization of a cycloaliphatic epoxy resin with arylsulfonium salts. J Polym Sci A 45:16–25 .
35. Fernández-Francos, X, Salla, JM, Pérez, G, Mantecón, A, Serra, A, Ramis, X 2009 New thermosets obtained by thermal and UV-induced cationic copolymerization of DGEBA with 4-phenyl-γ-butyrolactone. Macromol Chem Phys 210:1450–1460 .
36. Aspinall, HC, Dwyer, JLM, Greeves, W, McIver, EG, Woolley, JC 1998 Solubilized lanthanide triflates: Lewis acid catalysis by polyether and poly(ethylene glycol) complexes of Ln(OTf)3. Organometallics 17:1884–1888 .