New polyurethane chemically crosslinked networks containing silica were synthesized by both Diels–Alder polymerization and Michael addition reaction. Structural characterization of the products was evidenced by proton nuclear magnetic resonance and attenuated total reflectance in conjunction with Fourier transform infrared spectroscopy techniques. Differential scanning calorimetry was used to demonstrate the thermally remendable character of the materials obtained through Diels–Alder polymerization. The influence of increasing silica content on the glass transition temperatures was studied. It was observed that the glass transition temperatures increased with increasing silica content. Absolute heat capacities and crosslinking densities were determined for the thermoreversible materials. A comparison between materials obtained through Diels–Alder process and Michael addition method was studied. A kinetic study was conducted via an isoconversional method. Morphological studies were conducted by atomic force microscopy technique.
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Teramoto N, Arai Y, Shibata M. Thermo-reversible Diels–Alder polymerization of difurfurylidene trehalose and bismaleimides. Carbohydr Polym. 2006;64:78–84.
Carlson HC, Goretta KC. Basic materials research programs at the US air force office of scientific research. Mater Sci Eng Part B. 2006;132:2–7.
Dry CM, Sottos NR. Passive smart self-repair in polymer matrix composite materials. Conference on recent advances in adaptive and sensory materials and their applications. Virginia: Technomic; 1992. p. 438–444.
Dry CM. Passive smart materials for sensing and actuation. J Intell Mater Sys Struct. 1993;4:420–5.
Schmets AJM, van der Zwaag S. Proceedings of the first international conference on self healing materials. In: Supplement to springer series in materials science. Noordwijk: Springer; 2007.
White SR, Sottos NR, Geubelle PH, Moore JS, Kessler MR, Sriram SR, Brown EN, Viswanathan S. Autonomic healing of polymer composites. Nature. 2001;409:794–7.
Endo T, Nagai D. A novel construction of ring-opening polymerization and chemical recycling system. Macromol Symp. 2005;226:79–86.
Sassw F, Emig G. Chemical recycling of polymers. Chem Eng Technol. 1998;21:777–89.
Chen X, Wudl F, Mal AK, Shen H, Nutt SR. New thermally remendable highly cross-linked polymeric materials. Macromolecules. 2003;36:1802–7.
Chino K, Ashiura M. Thermoreversible crosslinking rubber using supramolecular hydrogen bonding networks. Macromolecules. 2001;34:9201.
Gheneim R, Perez-Berumen C, Gandini A. Diels–Alder reactions with novel polymeric dienes and dienophiles: synthesis of reversibly cross-linked elastomers. Macromolecules. 2002;35:7246–53.
Liu YL, Chen YW. Thermally reversible cross-linked polyamides with high toughness and self-repairing ability from maleimide- and furan-functionalized aromatic polyamides. Macromol Chem Phys. 2007;208:224–32.
Brand T, Klapper M. Control of viscosity through reversible addition of telechelics via repetitive Diels–Alder reaction in bulk. Des Monomer Polym. 1999;2:287–309.
Diakoumakos CD, Mikroyannidis JA. Polyimides derived from Diels–Alder polymerization of furfuryl-substituted maleamic acids or from the reaction of bismaleamic with bisfurfurylpyromellitamic acids. J Polym Sci Part A. 1992;30:2559–67.
Gandini A, Belgacem MN. Furan in polymer chemistry. Prog Polym Sci. 1997;22:1203–379.
Goiti E, Huglin MB, Rego JM. Some observations on the copolymerization of styrene with furfuryl methacrylate. Polymer. 2001;42:10187–93.
Kennedy JP, Carlson GM. Synthesis, characterization, and Diels–Alder extension of cyclopentadiene telechelic polyisobutylene. IV. α,ω-Di(3-cyclopentadienyl-propyldimethylsilyl)polyisobutylene. J Polym Sci Polym Chem Ed. 1983;21:3551–61.
Laita H, Boufi S, Gandini A. The application of the Diels–Alder reaction to polymers bearing furan moieties. 1. Reactions with maleimides. Eur Polym J. 1997;33:1203–11.
Mikroyannidis JA. Synthesis and Diels–Alder polymerization of furfurylidene and furfuryl-substituted maleamic acids. J Polym Sci Part A. 1992;30:125–32.
Gaina V, Ursache O, Gaina C, Buruiana E. Novel thermally-reversible epoxy-urethane networks. Des Monomer Polym. 2012;15:63–73.
Vera-Graziano R, Hernandez-Sanchez F, Cauich-Rodriguez JV. Study of crosslinking density in polydimethylsiloxane networks by DSC. J Appl Polym Sci. 1995;55:1317–27.
Furukawa GT, Douglas TB, McCloskey RE, Ginnings DC. Thermal properties of aluminum oxide from 0 K to 1200 K. J Res Nat Bur Stand. 1956;57:67–82.
van Ekeren PJ. Thermodynamic background to thermal analysis and calorimetry. In: Brown ME, editor. Handbook of thermal analysis and calorimetry. Amsterdam: Elsevier; 1998. p. 90–1.
Haines PJ, Reading M, Wilburn FW. Differential thermal analysis and differential scanning calorimetry. In: Brown ME, editor. Handbook of thermal analysis and calorimetry. Amsterdam: Elsevier; 1998. p. 340–1.
Doyle CD. Estimating isothermal life from thermogravimetric data. J Appl Polym Sci. 1962;6:639–42.
Rabek JF, editor. In: Experimental methods in polymer chemistry. Chichester: Wiley; 1980. p. 241.
Hagiwara T, Suzuki I, Takeuchi K, Hamana H, Narita T. Synthesis and polymerization of N-(4-vinylphenyl)maleimide. Macromolecules. 1991;24:6856–8.
Wu W, Wang D, Wang P, Zhu P, Ye C. Thermally stable nonlinear optical polyimide functionalized by N,N-diallylamino-substituted chromophore. J Appl Polym Sci. 2000;77:2939–47.
Ozawa T. A new method of analysing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881–6.
Opfermann J, Kaisersberger E. An advantageous variant of the Ozawa–Flynn–Wall analysis. Thermochim Acta. 1992;203:167–75.
Hatakeyama T, Liu Z, editors. Handbook of thermal analysis. Chichester: Wiley; 1998. p. 47–8.
Hatakeyama T, Liu Z, editors. Handbook of thermal analysis. Chichester: Wiley; 1998. p. 359–60.
Tian Q, Rong MZ, Zhang MQ, Yuan YC. Optimization of thermal remendability of epoxy via blending. Polymer. 2010;51:1779–85.
Yu YY, Chen CY, Chen WC. Synthesis and characterization of organic–inorganic hybrid thin films from poly(acrylic) and monodispersed colloidal silica. Polymer. 2003;44:593–601.
Kavitha AA, Singha NK. Smart “all acrylate” ABA triblock copolymer bearing reactive functionality via atom transfer radical polymerization (ATRP): demonstration of a “click reaction” in thermoreversible property. Macromolecules. 2010;43:3193–205.
Chen X, Dam MA, Ono K, Mal A, Shen H, Nutt SR, Sheran K, Wudl F. A thermally re-mendable cross-linked polymeric material. Science. 2002;295:1698–702.
Zhang Y, Broekhuis AA, Picchioni F. Thermally self-healing polymeric materials: the next step to recycling thermoset polymers? Macromolecules. 2009;42:1906–12.
Kavitha AA, Singha NK. Atom-transfer radical copolymerization of furfuryl methacrylate (FMA) and methyl methacrylate (MMA): a thermally-amendable copolymer. Macromol Chem Phys. 2007;208:2569–77.
Wouters M, Craenmehr E, Tempelaars K, Fischer H, Stroeks N, van Zanten J. Preparation and properties of a novel remendable coating concept. Prog Org Coat. 2009;64:156–62.
Srikant SK, Arjumand AK, Mrityunjaya IA, Mahadevappa YK. Synthesis and characterization of hybrid membranes using poly(vinyl alcohol) and tetraethylorthosilicate for the pervaporation separation of water–isopropanol mixtures. J App Polym Sci. 2004;94:1304–15.
Hsu YG, Lin FJ. Organic-inorganic composite materials from acrylonitrile–butadiene–styrene copolymers and silica through an in situ sol–gel process. J Appl Polym Sci. 2000;75:275–83.
Carraher CE Jr, Pittman CU Jr. Industrial polymers handbook. Weinheim: Wiley; 2001. p. 1284.
Jothibasu S, Kumar AA, Alagar M. Synthesis of maleimide substituted polystyrene–silica hybrid utilizing Michael addition reaction. J Sol Gel Sci Technol. 2007;4:337–45.
Pawelec B, Fierro JLG. Applications of thermal analysis in the preparation of catalysts and in catalysis. In: Brown ME, Gallagher PK, editors. Handbook of thermal analysis and calorimetry. Amsterdam: Elsevier; 2003. p. 178.
Galwey AK, Brown ME. Kinetic background to thermal analysis and calorimetry. In: Brown ME, editor. Handbook of thermal analysis and calorimetry. Amsterdam: Elsevier; 1998. p. 169–71.
Galwey AK, Brown ME. Kinetic background to thermal analysis and calorimetry. In: Brown ME, editor. Handbook of thermal analysis and calorimetry. Amsterdam: Elsevier; 1998. p. 190–4.
Opferman J. Kinetic analysis using multivariate non-linear regression. J Therm Anal Calorim. 2000;60:641–58.
Wahab MA, Kim I, Ha CS. Microstructure and properties of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA)-p-phenylene diamine (PDA) polyimide/poly(vinylsilsesquioxane) hybrid nanocomposite films. J Polym Sci Part A. 2004;42:5189–519.
This study was supported by a grant of the Romanian National Authority for Scientific Research, CNCS–UEFISCDI, project number PN-II-ID-PCE-2011-3-0187.
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Varganici, CD., Ursache, O., Gaina, C. et al. Studies on new hybrid materials prepared by both Diels–Alder and Michael addition reactions. J Therm Anal Calorim 111, 1561–1570 (2013). https://doi.org/10.1007/s10973-012-2532-y