Abstract
Ring-opening metathesis polymerization (ROMP), ring-closing metathesis (RCM) and ring-opening cross metathesis (RO/CM) are interesting methods to synthesize polymers with attractive mechanical and electrical properties, and specialty chemicals. Ruthenium and osmium based catalysts are water stable and possess a remarkable tolerance towards most functional groups. Whereas the first generation of well defined ruthenium based ROMP catalysts, cationic complexes like Ru(H2O)6tos2 (tos=toluene-4-sulfonate) and Ru(arene)2tos2 (activated by UV-irradiation) showed much lower reactivities as compared to “activated” early transition metal catalysts, Ru-phosphine complexes like RuCl2(p-MeC6H4CHMe2)(PCy3) (1, Cy=cyclohexyl) developed by Ciba SC and later Ru-phoshine-carbenes, developed by Grubbs et al. and Ciba SC are able to polymerize a large range of cycloolefins including DCPD (in technical quality and in mixtures with additives and fillers) very efficiently. The new classes of ruthenium carbene complexes are accessible by a novel synthesis which avoids the use of hydrogen gas and is therefore easy to scale up. Catalyst reactivities in ROMP of different monomers (characterized in terms of their turn-over frequencies (TOF) and compared with other catalysts for olefin polymerization), in RCM and RO/CM are very much dependent on the ligand sphere and the type of monomer used. Polymerizations were conducted in bulk, solution and dispersion with a large range of non-functionalized and functionalized 2-norbornene derivatives to obtain linear and crosslinked homo- and copolymers (block and random) which may find useful applications in the near future.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
Similar content being viewed by others
References
Ivin, K.J. and Mol, J.C. (1996) Olefin Metathesis and Metathesis Polymerization, Academic Press, London.
Bell, A. (1992) J. Mol. Catal. 76, 165.
Goodall, B.L., Kroenke, W.J., Minchak, R.J. and Rhodes, L.F. (1993) J. Appl. Polym. Sci. 47, 607.
Schaverien, C.J., Dewan, J.C. and Schrock, R.R. (1986) J. Am. Chem. Soc. 108, 2771.
Novak, B.M. and Grubbs, R.H. (1988) J. Am. Chem. Soc. 110, 960.
In fact, it was reported that DCPD is a poison for ruthenium-initiated ROMP: Tanielian, C., Kiennemann, A. and Osparpucu, T. (1979) Can. J. Chem. 57, 2022.
Hafner, A., Muehlebach, A. and van der Schaaf, P.A. (1997) Angew. Chem. Int. Ed. Engl. 36, 2121.
Hafner, A., van der Schaaf, P.A. and Muehlebach, A. US-P 5, 998,326 (Ciba S.C.), Prio: 23.5.97.
Irgafos TNPP is a liquid processing stabilizer for styrenics, PUR and elastomers.
Schwab, P., France, M.B., Ziller, J.W. and Grubbs, R.H. (1995) Angew. Chem. 107, 2179; (1995) Angew. Chem. Int. Ed. Engl. 34, 2039.
Muehlebach, A., van der Schaaf, P.A. and Hafner, A. EP 891, 384 (Ciba S.C.), prio. 4.4.96.
Gruenwald, C., Gevert, O., Wolf, J., Gonzales-Herrero, P. and Werner, H. (1996) Organometallics, 15, 1960; Wolf, J., Stuer, W., Gruenwald, C., Werner, H., Schwab, P. and Schulz, M. (1998) Angew. Chem., Int. Ed. Engl.37, 1124.
Wilhelm, T.E., Belderrain, T.R., Brown, S.N. and Grubbs, R.H. (1997) Organolmetallics 16, 3867; Grubbs, R.H., Belderrain, T.R., Brown, S.N. and Wilhelm, T.E. WO Pat. 98 21, 214 (CalTech) [Chem. Abstr. 1998, 129, 41513].
van der Schaaf, P.A., Kolly, R., Hafner, A. and Muehlebach, A. EP Pat. 839,821 (Ciba SC) [Chem. Abstr. 1998, 129, 41274].
Burrow, T., Sabo-Etienne, S. and Chaudret, B. (1995) Inorg. Chem. 34, 2470.
Esteruelas, M.A., Lahoz, F.J., Onate, E., Oro, L.A., Valero, C. and Zeier, B. (1995) J. Am. Chem. Soc. 117, 7935.
van der Schaaf, P.A., Kolly, R. and Hafner, A. (2000) Chem. Commun. 1045.
Similar results were obtained earlier with 2-norbornene mono-and diesters.
See e.g. Kanaoka, S. and Grubbs, R.H. (1995) Macromolecules 28, 4707.
van der Schaaf, P.A., Kolly, R., Kirner, H.-J., Rime, F., Mühlebach, A. and Hafner, A. J. Organomet. Chem., in press.
Tetradecylnorbornene (C14-NBE; yield: 22%, liquid, b.p. 125-130°C at p=0.018 mbar, m.p. +4°C, GCpurity: >95%, mixture of isomers), a new norbornene-type monomer with long alkyl chain, was synthesized from 1-hexadecene and cyclopentadiene (CDP). It is an interesting (co)monomer for ROMP and especially vinyl-addition polymerization, where the insolubility of the resulting polymers poses serious problems to polymer analysis. C14-TD (yield: 13%, purity: >80%, mixture of isomers) was isolated as by-product.
Dias, E.L., Nguyen, S.T. and Grubbs, R.H. (1997) J. Am. Chem. Soc. 119, 3887.
a) Lynn, D.M., Mohr, B. and Grubbs, R.H. (1998) Polym. Prepr. 39, 278. b) Lynn, D.M., Mohr, B. and Grubbs, R.H. (1998) J. Am. Chem. Soc. 120, 1627. c) Lynn, D.M, Dias, E.L., Grubbs, R.H. and Mohr, B.Patent WO 99/22865.
van der Schaaf, P.A., Mühlebach, A. and Hafner, A. Patent WO 99/00397.
Rinehart, R.E. (1969) J. Polym. Sci. Part C., 27, 7.
Lynn, D.M., Kanaoka, S. and Grubbs, R.H. (1996) J. Am. Chem. Soc. 118, 784.
In a typical example 431 g ethylene glycol (Merck, p.a.) was mixed in a 750 ml reaction vessel with mechanical stirring and N2 inlet/outlet with 2.66 g of a 50% solution of lauryl-dimethyl-benzylammonium chloride in water (cationic emulgator from Henkel) and 12.92 g hydroxypropyl cellulose (protecting colloide, Klucel E, Aqualon). The mixture was heated to 100°C for 5 min (to homogenize) and cooled down to R.T. and purged with nitrogen. Catalysts 1 (100 mg) and 8 (33 mg), dissolved in methylenechloride, were mixed with 33.33 g DCPD (Shell, 94%), containing 66 mg Irganox 1076 (antioxidant from Ciba SC). The catalyst/monomer mixture was than added to the ethyleneglycol/emulgator/protecting colloide mixture and stirred (ca. 700 rpm) 20 min at R.T., 1 h at 45°C, 2h at 65°C, 1h at 85°C and 2.5 h at 105°C. After cooling to R.T., the reaction mixture was filtered, washed with water, the solid polymer stirred 30 min with 300 ml water and again filtered. The poly(DCPD) powder was than dried 14 h at 50°C in vacuo (p<0.1 mbar). Yield: 27.3 g (82%) of a white powder. Elemental analysis: calc.: C 90.84% H 9.15%, found: C 90.11% H 9.33%.
Muehlebach, A., van der Schaaf, P.A., Hafner, A. and Setiabudi, F. (1998) J. Mol. Catal. 132, 181.
Muehlebach, A. unpublished results.
Delia Martina, A., Hilborn, J.G. and Mühlebach, A. (2000) Macromolecules 33, 2916.
The initiation step is probably much faster, because the active species has not to be generated in situ (by ligand exchange and oxidative addition).
Kurosawa, H., Emoto, M., Urabe, A., Miki, K. and Kasai, N. (1985) J. Am. Chem. Soc. 107, 8253.
1 was designed as cheap, latent catalyst for the polymerization of DCPD in the bulk. It is not suitable for the polymerization of functionalized cycloolefins in solution.
It turned out that the right choice of solvent is extremely important to obtain living ROMP. Chlorinated hydrocarbons are best (e.g. chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, CH2Cl2, 1,1,2-trichloroethane; yields: >90%; PDI:<1.3), followed by esters (e.g. ethylacetate, γ-butyrolactone; yields: 70-80%; PDI: 1.2-1.5) and ethers (dimethoxyethane, THF; yields: <40%; PDI: 1.3-1.5). Ketones (e.g. methyl-ethylketone, cyclopentanone), amides (e.g. DMF, N-methyl-pyrrolidone) and sulfoxides (e.g. sulfolane, DMSO) gave no isolatable yields.
For a good review article see Schuster, M. and Blechert, S. (1997) Angew. Chem. 109, 2124.
Nicolaou, K.C., He, Y., Vourloumis, D. and Vallberg, H. (1997) J. Am. Chem. Soc. 119, 7960.
Schneider, M.F., Lucas, N., Velder, J. and Blechert, S. (1997) Angew. Chemie 109, 257.
van der Schaaf, P.A., Mühlebach, A., Hafner, A. and Kolly, R. Patent WO 99/29701 (prio: 4.12.97).
Muehlebach, A., Prétôt, R. and van der Schaaf, P.A. manuscript in preparation.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2002 Springer Science+Business Media Dordrecht
About this chapter
Cite this chapter
Muhlebach, A., Van Der Schaaf, P.A., Hafner, A., Kolly, R., Rime, F., Kimer, HJ. (2002). Ruthenium Catalysts for Ring-Opening Metathesis Polymerization (ROMP) and Related Chemistry. In: Khosravi, E., Szymanska-Buzar, T. (eds) Ring Opening Metathesis Polymerisation and Related Chemistry. NATO Science Series, vol 56. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0373-5_3
Download citation
DOI: https://doi.org/10.1007/978-94-010-0373-5_3
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-0559-6
Online ISBN: 978-94-010-0373-5
eBook Packages: Springer Book Archive