Abstract
Driven by the desire to find an alternative way of vulcanizing elastomers without sulfur, researchers have widely explored ionic crosslinking techniques. The opportunity was taken to play with the functionality of the host polymer and its modification process to develop nanostructured ionic elastomers. Neutralization of polar elastomers by various divalent metal cations has been the route most employed for fabrication of this class of material. Ionic association or aggregation on the molecular level results in microphase separation of certain regions and, hence, enables easier processing. Thermally labile ionic domains introduced into the network make the entire material thermoresponsive and, therefore, it is possible to obtain reversible transition of dynamic mechanical properties. The unique network structure of these materials has led to outstanding physical properties that have not been achieved so far for conventional sulfidic networks. Consequently, many multifunctional and smart materials have been envisaged and designed using these systems. A detailed overview is provided on the various nanostructured ionic elastomers developed over the years. It would not be exaggerating to mention in the context of the discussion that nanostructured ionic elastomers will definitely open up new horizons in materials research.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Treloar LRG (2005) The physics of rubber elasticity. OUP, Oxford
Flory PJ (1985) Molecular theory of rubber elasticity. Polym J 17:1–12
Hofmann W (1989) Rubber technology handbook. Oxford University Press, Oxford
Schüssele AC, Nübling F, Thomann Y, Carstensen GB, Speck T, Mülhaupt R (2012) Macromol Mater Eng 297:411–419
Rees RW, Vaughan DJ (1965) Polym Prepr (Am Chem Soc Div Polym Chem) 6:287
Eisenberg A (1970) Clustering of ions in organic polymers—a theoretical approach. Macromolecules 3:147–154
Basu D, Das A, Stöckelhuber KW, Jehnichen D, Formanek P, Sarlin E, Vuorinen J, Heinrich G (2014) Evidence for an in-situ developed polymer phase in ionic elastomers. Macromolecules 47(10):3436–3450
MacKnight WJ, Lundberg RD (1984) Elastomeric ionomers. Rubber Chem Technol 57(3):652–663
Eisenberg A, Hird B, Moore RB (1990) A new multiplet-cluster model for the morphology of random ionomers. Macromolecules 23:4098–4107
Hird B, Eisenberg A (1992) Sizes and stabilities of multiplets and clusters in carboxylated and sulfonated styrene ionomers. Macromolecules 25:6466–6474
MacKnight WJ (1987) Available ionomers. In: Pineri M, Eisenberg A (eds) Structure and properties of ionomers. NATO science series C: mathematical and physical sciences, vol 198. Reidel, Dordrecht, pp 1–9
MacKnight WJ, Earnest TR (1981) Macromol Rev 16:41
Bazuin GC, Eisenberg A (1981) Ind Eng Chem Prod Res Dev 20:271
Khokhlov AR, Dormidontova EF (1997) Self-organization in ion-containing polymer systems. Phys Usp 40:109–124
Nyrkova IA, Khokhlov AR, Doi M (1993) Microdomains in block copolymers and multiplets in ionomers: parallels in behavior. Macromolecules 26:3601–3610
Eisenberg A (1967) Ionic forces in polymers. Adv Polym Sci 5:59–112
McGrath JE (ed) (1981) Anionic polymerization: kinetics, mechanisms, and synthesis. ACS Symposium Series, vol 166. American Chemical Society, Washington
Basu D, Das A, Stöckelhuber KW, Wagenknecht U, Heinrich G (2014) Advances in layered double hydroxide (LDH)-based elastomer composites. Prog Polym Sci 39:594–626
Masala O, Seshadri R (2004) Synthesis routes for large volumes of nanoparticles. Annu Rev Mater Res 34:41–81
Lundberg RD, Markowski HS (1980) A comparison of sulfonate and carboxylate ionomers. In: Eisenberg A (ed) Ions in polymers. ACS advances in chemistry series, vol 187. American Chemical Society, Washington, pp 21–36
Jenkins DK, Duck EW (1975) In: Holliday L (ed) Ionic polymers. Halstead Press, Wiley, New York (chap. 3)
Das A, Sallat A, Böhme F, Suckow M, Basu D, Wiessner S, Stöckelhuber KW, Voit B, Heinrich G (2015) Ionic modification turns commercial rubber into a self-healing material. ACS Appl Mater Interfaces 7:20623–20630
Basu D (2015) Role of zinc containing compounds in nitrile rubber based micro-and nanocomposites. Thesis in TU Dresden, Germany
Ibarra L, Marcos-Fernández A, Alzorriz M (2002) Mechanistic approach to the curing of carboxylated nitrile rubber (XNBR) by zinc peroxide/zinc oxide. Polymer 43:1649–1655
Ibarra L, Alzorriz M (2003) Ionic elastomers based on carboxylated nitrile rubber and calcium oxide. J Appl Polym Sci 87:805–813
Ibarra L, Alzorriz M (2007) Ionic elastomers based on carboxylated nitrile rubber and magnesium oxide. J Appl Polym Sci 103:1894–1899
Tungchaiwattana S, Musa MS, Yan J, Lovell PA, Shaw P, Saunders BR (2014) The role of acrylonitrile in controlling the structure and properties of nanostructured ionomer films. Soft Matter 10:4725–4734
Chakraborty SK, Bhowmick AK, De SK (1981) Mixed cross-link systems in elastomers. J Macromol Sci Polym Rev 21:313–332
Jong L (2005) Viscoelastic properties of ionic polymer composites reinforced by soy protein isolate. J Polym Sci B Polym Phys 43:3503–3518
Malmierca MA, González-Jiménez A, Mora-Barrantes I, Posadas P, Rodríguez A, Ibarra L, Nogales A, Saalwächter K, Valentín JL (2014) Characterization of network structure and chain dynamics of elastomeric ionomers by means of 1H low-field NMR. Macromolecules 47:5655–5667
Kurian T, Khastgir D, De PP, Tripathy DK, De SK, Peiffer DG (1995) Reinforcement of EPDM-based ionic thermoplastic elastomer by carbon black. Polymer 36:3875–3884
Markowski HS, Lundberg RD, Westerman L, Bock J (1980) Synthesis and properties of sulfonated EPDM. In: Eisenberg A (ed) Ions in polymers. ACS, vol 187. American Chemical Society, Washington, pp 3–19
Kurian T, De PP, Tripathy DK, De SK, Peiffer DG (1996) Effect of clay on properties of ionic thermoplastic elastomer based on EPDM. J Appl Polym Sci 62:1729–1734
Ghosh SK, Bhattacharya AK, De PP, Khastagir D, De SK (2001) Effect of zinc stearate on properties of melt processable ionomer based on sodium salt of sulfonated maleated EPDM rubber. Plast Rubber Compos 1:16–22
Yano S, Nagao N, Hattori M, Hirasawa E, Tadano K (1992) Dielectric relaxations of ethylene ionomers. Macromolecules 25:368
Yano S, Tadano K, Nagao N, Kutsumizu S, Tachino H, Hirasawa E (1992) Dielectric relaxation studies on water absorption of ethylene ionomers. Macromolecules 25:7168
MacKnight WJ, McKenna LW, Read BE (1968) Properties of ethylene-methacrylic acid copolymers and their sodium salts: mechanical relaxations. J Appl Phys 38:4208
Mandal UK, Tripathy DK, De SK (1995) Effect of silica filler on dynamic mechanical properties of ionic elastomer based on carboxylated nitrile rubber. J Appl Polym Sci 55:1185–1191
Mandal UK, Tripathy DK, De SK (1993) Moving die rheometry and dynamic-mechanical studies on the effect of reinforcing carbon-black filler on ionomer formation during cross-linking of carboxylated nitrile rubber by zinc-oxide. Polymer 34:3832–3836
Mandal UK, Tripathy DK, De SK (1995) Effect of reinforcing carbon black fillers on dynamic mechanical properties of ionic elastomer based on carboxylated nitrile rubber. Plast Rubber Comp Proc Appl 24:19–25
Datta S, De SK, Kontos EG, Wefer JM (1996) Ionic thermoplastic elastomer based on maleated EPDM rubber. I. Effect of zinc stearate. J Appl Polym Sci 61:177–186.
Navratil M, Eisenberg A (1984) Ion clustering and viscoelastic relaxation in styrene-based ionomers. III. Effect of counterions, carboxylic groups, and plasticizers. Macromolecules 7:84–89
Weiss RA, Fitzerald JJ, Kim D (1991) Viscoelastic behavior of plasticized sulfonated polystyrene ionomers. Macromolecules 24:1064–1070
Lundberg RD (1987) Ionomer solution behavior. In: Pineri M, Eisenberg A (eds) Structure and properties of ionomers. NATO science series C, vol 198. Reidel, Dordrecht, pp 387–397
Agarwal PK, Peiffer DG (1987) Viscoelastic behaviour of blends of ionic thermoplastic elastomers and their precursors. Polym Commun 28:186–190
van der Mee MAJ, I’Abee RMA, Portale G, Goossens JGP, van Duin M (2008) Synthesis, structure, and properties of ionic thermoplastic elastomers based on maleated ethylene/propylene copolymers. Macromolecules 41:5493–5501
Brenner D, Lundberg RD (1977) Novel flexible foams based on an ionic elastomer. J Cell Plast 13:270–275
Drake EN (1994) Polym Prepr Am Chem Soc Div Polym Chem 35:14
Jaudouin O, Robin JJ, Lopez-Cuesta JM, Perrin D, Imbert C (2012) Ionomer-based polyurethanes: a comparative study of properties and applications. Polym Int 61:495–510
Dieterich D, Keberle W, Wilt H (1970) Polyurethane ionomers, a new class of block polymers. Angew Chem Int Ed Engl 9:40–50
Hwang KKS, Yang C-Z, Cooper SL (1981) Properties of polyether-polyurethane zwitterionomers. Polym Eng Sci 21:1027–1036
Yang C-Z, Hwang KKS, Cooper SL (1983) Morphology and properties of polybutadiene-and polyether-polyurethane zwitterionomers. Makromol Chem 184:651–668
Lee JC, Kim BK (1994) Basic structure–property behavior of polyurethane cationomers. J Polym Sci A Polym Chem 32:1983–1989
Estes GM, Cooper SL, Tobolsky AV (1970) J Macromol Sci Rev Macromol Chem 4:313
Agganval SL (ed) (1970) Block polymers. Plenum Press, NewYork
Noshay A, McGrath JE (eds) (1973) Block copolymers. Wiley, New York
Cooper SL, Estes GM (eds) (1979) Multiphase polymers. Adu. Chem. Ser. 176, American Chemical Society, Washington
Clough SB, Schneider NS (1968) J Macromol Sci Phys B2:553
Clough SB, Schneider NS, King AO (1968) J Macromol Sci Phys B2:641
Lee D, Register RA, Yang C, Cooper SL (1988) MDI-based polyurethane ionomers. 1. New small-angle X-ray scattering model. Macromolecules 21:998–1004
Lee D, Register RA, Yang C, Cooper SL (1988) MDI-based polyurethane ionomers. 2. Structure-property relationships. Macromolecules 21:1005–1008
Kim B, Yang J, Yoo S, Lee J (2003) Waterborne polyurethanes containing ionic groups in soft segments. Colloid Polym Sci 281:461–468
Mondal S, Hu JL (2006) Structural characterization and mass transfer properties of nonporous segmented polyurethane membrane: Influence of hydrophilic and carboxylic group. J Memb Sci 274:219–226
Nierzwicki W, Rutkowska M (1986) Ionic interactions and microphase separation in urethane elastomers. Polym Commun 27:327–329
Lee BS, Chun BC, Chung YC, Sul KI, Cho JW (2001) Structure and thermomechanical properties of polyurethane block copolymers with shape memory effect. Macromolecules 34:6431–6437
Chwang CP, Lee SN, Kuo YM, Chao S, Chao DY (2002) On the study of polyurethane ionomer-Part I. Polym Adv Technol 13:285–292
Chwang CP, Lee SN, Kuo YM, Chao S, Chao DY (2002) On the study of polyurethane ionomer-Part II. Polym Adv Technol 13:293–300
Kim BY, Lee SY, Lee JS, Baek SH, Choi YJ, Lee JO, Xu M (1998) Polyurethane ionomers having shape memory effects. Polymer 39:2803–2808
Gogolewski S (1989) Selected topics in biomedical polyurethanes: a review. Colloid Polym Sci 267:757–785
Barbucci R, Benvenuti M, Dal Maso G, Nocentini M, Tempesti F, Losi M (1989) Synthesis and physicochemical characterization of a new material (PUPA) based on polyurethane and poly(amido-amine) components capable of strongly adsorbing quantities of heparin. Biomaterials 10:299–308
Barbucci R, Magnani A (1989) Physiochemical characterization and coating of polyurethane with a new heparin-adsorbing material. Biomaterials 10:429–431
Bakker D, Van Blitterswijk CA, Hesseling SC, Koerten HK, Kuijpers W, Grote JJ (1990) Biocompatibility of a polyether urethane, polypropylene oxide, and a polyether polyester copolymer. A qualitative and quantitative study of three alloplastic tympanic membrane materials in the rat middle ear. J Biomed Mater Res 24:489–515
Bruin P, Jonkman MF, Meijer HJ, Pennings AJ (1990) A new porous polyetherurethane wound covering. J Biomed Mater Res 24:217–226
Faust R, Kennedy JP (1987) Living carbocationic polymerization IV. Living polymerization of isobutylene. J Polym Sci Polym Chem Ed 25:1847
Allen RD, Yilgor I, McGrath JE (1986) Studies on synthetic block ionomers. In: Eisenberg A, Baily FE (eds) Coulombic interactions in macromolecular systems. ACS symposium series, vol 302. American Chemical Society, Washington, pp 79–92
Weiss RA, Sen A, Willis CL, Pottick LA (1991) Block copolymer ionomers: 1. Synthesis and physical properties of sulfonated poly(styrene-ethylene/butylene-styrene). Polymer 32:1867–1874
WolImann D, Williams CE, Eisenberg A (1990) Small-angle X-ray scattering in “bottlebrush” ionomers. J Polym Sci Polym Phys Ed 28:1979
Storey RF, George SE, Nelson ME (1991) Star-branched block copolymer ionomers: synthesis, characterization, and properties. Macromolecules 24:2920–2930
Vanhest JCM, Baars MWPL, Elissan-Roman C, Van Genderen MHP, Meijer EW (1995) Acid-functionalized amphiphiles, derived from polystyrene-poly(propylene imine) dendrimers, with a pH-dependent aggregation. Macromolecules 28:6689–6691
Vargantwar PH, Shankar R, Krishnan AS, Ghosh TK, Spontak RJ (2011) Exceptional versatility of solvated block copolymer/ionomer networks as electroactive polymers. Soft Matter 7:1651–1655
Meng FB, Zhang BY, Liu LM, Zang BL (2003) Liquid-crystalline elastomers produced by chemical crosslinking agents containing sulfonic acid groups. Polymer 44:3935–3943
Vuillaume PY, Galin JC, Bazuin CG (2001) Ionomer and mesomorphic behavior in a tail-end, ionic mesogen-containing, comblike copolymer series. Macromolecules 34:859–867
Bualek S, Kapitza R (1988) Orientability of crosslinked and of chiral liquid crystalline polymers. Mol Cryst Liq Cryst 155:47–56
Meng FB, Zhang BY, Jia YG, Yao DS (2005) Effect of ionic aggregates of sulfonated groups on the liquid crystalline behaviours of liquid crystalline elastomers. Liq Cryst 32:183–189
Paeglis AU, O'Shea FX (1988) Thermoplastic elastomer compounds from sulfonated EPDM ionomers. Rubber Chem Technol 61:223–237
Nogueira AF, Alonso-Vante N, De Paoli M-A (1999) Solid-state photoelectrochemical device using poly(o-methoxy aniline) as sensitizer and an ionic conductive elastomer as electrolyte. Synth Met 105:23–27
Telnov AV, Zavyalov NV, AKhokhlov Y, Sitnikov NP, Smetanin ML, Tarantasov VP, Shadrin DN, Shorikov IV, Liakumovich AL, Miryasova FK (2002) Radiation degradation of spent butyl rubbers. Radiat Phys Chem 63:245–248
Hohlbein N, Pelzer T, Nothacker J, von Tapavicza M, Nellesen A, Datta H, Schmidt AM (2013) Self-healing processes in ionomeric elastomers. In: ICSHM 2013: Proceedings of the 4th international conference on self-healing materials, Ghent, Belgium, 16–20 June 2013. Magnel Laboratory for Concrete Research, Ghent, pp 680–683
Chen B, Lu JJ, Yang CH, Yang JH, Zhou J, Chen YM, Suo Z (2014) Highly stretchable and transparent ionogels as nonvolatile conductors for dielectric elastomer transducers. Appl Mater Interfaces 6:7840–7845
Yu X, Rajamani R, Stelson K, Cui T (2006) Carbon nanotube-based transparent thin film acoustic actuators and sensors. Sens Actuat A 132:626–631
Shian S, Diebold RM, Clarke DR (2013) Tunable lenses using transparent dielectric elastomer actuators. Opt Express 21:8669–8676
Yu L, Madsen FB, Hvilsted S, Skov AL (2015) Dielectric elastomers, with very high dielectric permittivity, based on silicone and ionic interpenetrating networks. RSC Adv 5:49739–49747
Lendlein A, Kelch S (2002) Shape-memory polymers. Angew Chem Int Ed 41:2034–2057
Malmierca MA, Mora-Barrantes I, Posadas P, González-Jiménez A, Rodríguez A, Ibarra LM, Valentín JL (2013) Development of ionic elastomers with shape memory effect. In: Gil-Negrete N, Alonso A (eds) Constitutive models for rubber VIII. CRC, Boca Raton, pp 689–692
Cai W, Liu L (2008) Shape-memory effect of poly (glycerol-sebacate) elastomer. Mater Lett 62:2171–2173
Zia KM, Zuber M, Barikani M, Bhatti IA, Khan MB (2009) Surface characteristics of chitin-based shape memory polyurethane elastomers. Colloids Surf B Biointerfaces 72:248–252
Weiss RA, Izzo E, Mandelbaum S (2008) New design of shape memory polymers: mixtures of an elastomeric ionomer and low molar mass fatty acids and their salts. Macromolecules 41:2978–2980
Dong J, Weiss RA (2011) Shape memory behavior of zinc oleate-filled elastomeric ionomers. Macromolecules 44:8871–8879
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2016 Springer International Publishing Switzerland
About this chapter
Cite this chapter
Basu, D., Das, A., Stöckelhuber, K.W., Wießner, S. (2016). Nanostructured Ionomeric Elastomers. In: Stöckelhuber, K., Das, A., Klüppel, M. (eds) Designing of Elastomer Nanocomposites: From Theory to Applications. Advances in Polymer Science, vol 275. Springer, Cham. https://doi.org/10.1007/12_2016_8
Download citation
DOI: https://doi.org/10.1007/12_2016_8
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-47695-7
Online ISBN: 978-3-319-47696-4
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)