Abstract
Partial charge transfer between donor and acceptor groups has been used as a tool to physically structure silicone materials. In a first part, interactions between a single donor molecule, i.e. 9H-carbazole-9-ethanol, and a poly(dimethylsiloxane) functionalized on both chain-ends by acceptor groups, i.e. 3,5-dinitrobenzoate, were studied by DSC and UV-Vis analysis. The thermoreversibility of the interactions was likely demonstrated by UV-Vis analyses, which also showed a most favourable association of the complex for a 1/1 stoechiometry. The second part of this work deals with the synthesis of a triblock copolymer poly (2-(N-carbazolyl) ethyl methacrylate)-b-poly(dimethylsiloxane)-b-poly(2-(N-carbazolyl) ethyl methacrylate) by atom transfer radical polymerization in the presence of copper bromide and 1,1,4,7,10,10-hexamethyltriethylene tetramine in THF. The association of this triblock copolymer with the telechelic acceptor–based poly(dimethylsiloxane) used in the model study has been checked by rheology, which showed on heating and cooling a thermoreversible elastic/viscoelastic transition.
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References
Hohberg T, Schaefer O, Mueller J et al. (2003) Textiles coated or finished with polysiloxane-polyurea-polyurethane block copolymers (Wacker-Chemie G.m.b.H., Germany) EP1336683.
Kuepfer J, Schaefer O. (2004) Polysiloxane-polyurea-polyurethane block copolymers and their preparation (Wacker-Chemie G.m.b.H., Germany) US2004254325.
Scheim U, Ziche W. (2006) Crosslinkable siloxane urea copolymers for molding compositions (Wacker-Chemie G.m.b.H., Germany) WO2006010486.
Schaefer O, Weis J, Delica S et al. (2004) Thermoplastic silicone elastomers. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 45:714–715.
Brunsveld L, Folmer BJB, Meijer EW et al. (2001) Supramolecular Polymers. Chem. Rev. (Washington, D. C.) 101:4071–4097.
Binder WH, Zirbs R. (2007) Supramolecular polymers and networks with hydrogen bonds in the main- and side-chain. Adv. Polym. Sci. 207:1–78.
Bouteiller L. (2007) Assembly via hydrogen bonds of low molar mass compounds into supramolecular polymers. Adv. Polym. Sci. 207:79–112.
ten Brinke G, Ruokolainen J, Ikkala O. (2007) Supramolecular materials based on hydrogen-bonded polymers. Adv. Polym. Sci. 207:113–177.
Kozakiewicz J. (1998) Siloxane oligomer diols as potential intermediates for novel durable coatings. Surf. Coat. Int. 81:435–439.
Kozakiewicz J. (1996) Polysiloxaneurethanes: new polymers for potential coating applications. Prog. Org. Coat. 27:123–131.
Yilgor E, Tulpar A, Kara S et al. (2000) High strength silicone-urethane copolymers: synthesis and properties. ACS Symp. Ser. 729:395–407.
Tyagi D, Wilkes GL, Yilgor I et al. (1982) Siloxane-urea segmented copolymers. 2. Investigation of mechanical behavior. Polym. Bull. (Berlin) 8:543–550.
Yilgor I, Riffle JS, Wilkes GL et al. (1982) Siloxane-urea segmented copolymers. 1. Synthesis and characterization of model polymers from MDI and α,ω-bis(aminopropyl)polydimethylsiloxane. Polym. Bull. (Berlin) 8:535–542.
Yilgor E, Yilgor I. (2001) Hydrogen bonding: a critical parameter in designing silicone copolymers. Polymer, 42:7953–7959.
Yilgor E, Ekin Atilla G, Ekin A et al. (2003) Isopropyl alcohol: an unusual, powerful, green’ solvent for the preparation of silicone-urea copolymers with high urea contents. Polymer 44:7787–7793.
Sheth JP, Aneja A, Wilkes GL et al. (2004) Influence of system variables on the morphological and dynamic mechanical behavior of polydimethylsiloxane based segmented polyurethane and polyurea copolymers: a comparative perspective. Polymer 45:6919–6932.
Colombani O, Barioz C, Bouteiller L et al. (2005) Attempt toward 1D cross-linked thermoplastic elastomers: structure and mechanical properties of a new system Macromolecules 38:1752–1759.
Simionescu CI, Grigoras M. (1991) Macromolecular donor-acceptor complexes. Prog. Polym. Sci. 16:907–976.
Rodriguez-Parada JM, Percec V. (1986) Interchain electron donor-acceptor complexes: a model to study polymer-polymer miscibility? Macromolecules 19:55–64.
Simmons A, Natansohn A. (1991) Solid-state NMR study of charge-transfer interactions in polymer blends. Macromolecules 24:3651–3661.
Pugh C, Rodriguez-Parada JM, Percec V. (1986) The influence of molecular weight of the donor polymer on the solid-state behavior of interchain EDA complexes. J. Polym. Sci. Part A: Polym. Chem. 24:747–758.
Schneider HA, Cantow HJ, Massen U et al. (1982) Donor-acceptor complexation in macro-molecular systems. 2. Synthesis and viscoelastic properties of donor-acceptor complexed poly(methyl methacrylate)s and poly(butyl methacrylate)s. Polym. Bull. (Berlin, Germany) 7:263–270.
Schneider HA, Cantow HJ, Percec V. (1982) Donor-acceptor complexation in macromolecular systems. 1. Viscoelastic properties of polydonor-polyacceptor blends and of corresponding copolymers. Polym. Bull. (Berlin, Germany) 6:617–621.
Schneider HA, Cantow HJ, Percec V. (1982) Viscoelastic properties of poly-donor-poly-acceptor blends and of corresponding copolymers. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 23:203–204.
Zentel R, Wu J, Cantow HJ. (1985) Influence of electron-donor-acceptor complex formation on the melt viscosity of some poly(dimethylsiloxane)s. Makromol. Chem. 186:1763–1772.
Cojocariu G, Natansohn A. (2003) Perturbation of Charge-Transfer Complexes in Aqueous Solutions of PEG-DNB by Adding N-Ethylcarbazole and Li+ Cations. J. Phys. Chem. 107:5658–5665.
Zeng F, Shen Y, Zhu S, Pelton R. (2000) Synthesis and Characterization of Comb-Branched Polyelectrolytes. 1. Preparation of Cationic Macromonomer of 2-(Dimethylamino)ethyl Methacrylate by Atom Transfer Radical Polymerization. Macromolecules 33:1628–1635.
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Pouget, E., Ganachaud, F., Boutevin, B. (2008). Thermoreversible Crosslinking of Silicones Using Acceptor-Donor Interactions. In: Ganachaud, F., Boileau, S., Boury, B. (eds) Silicon Based Polymers. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8528-4_7
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DOI: https://doi.org/10.1007/978-1-4020-8528-4_7
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