Abstract
Material properties of olefin metathesis polymers made by thermal (ROMP) or photoinduced (PROMP) polymerization with ruthenium (II)-salts and the later developed ruthenium-phosphines as catalysts are described. The low oxidative stability was improved by copolymerization with so-called “build-in” antioxidants (AOs), i.e. hindered phenols or aromatic amines bearing 2-norbornene units.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsPreview
Unable to display preview. Download preview PDF.
References
Ciba-Geigy Co., Corporate Research, now, after the merger with Sandoz to form Novartis and the spinoff of the technical divisions, called Ciba Specialty Chemicals (Ciba SC).
Novak, B.M., Grubbs, R.H. (1998) J. Am. Chem. Soc. 110, 960.
Ru(H2O)6tos2 was first synthesized by our coworker P. Bernhard, university of Berne, Switzerland: Bernhard, P., Biner, M., Ludi, A. (1990) Polyhedron 9, 1095. We prepared up to 40 g batches of this catalyst at that time.
Mühlebach, A., Bernhard, P., Bühler, N., Karlen, T., Ludi, A. (1994) J. Mol. Catal. 90, 143.
See e.g. Ivin, K.J., Mol, J.C. Olefin Metathesis and Metathesis Polymerization, Academic Press 1997. Very rarely, some order of tacticity was observed in certain ROMP polymer structures but—so far—only with Schrock-type catalysts.
Vestenamer 6213, Huels Chemical Co, D-Marl, Germany.
30 mg Ru(H2O)6tos2 were dissolved in 20 ml EtOH/H2O and stirred 24 h with 2.0g poly(norbornene). After filtration and washing with EtOH and water, 500 ppm Ru were found in the polymer. Dissolving the polymer in toluene, precipitation into EtOH and drying gave still a Ru-content of 430 ppm.
Mühlebach, A. unpublished results.
Meier, H.R., Mühlebach, A. US-P. 5,852,090 (Ciba SC, CH-prio: 1.2.96).
Mühlebach, A., van der Schaaf, P.A., Hafner, A. DE 19,718,288 (Ciba SC, prio: 3.5.96).
Fatt, I. (1981) Intern. Contact Lens Clinic 9, 76. The Dk/L-values obtained at 35°C and 95% relative humidity are multiplied with the mean film thickness (L) to get Dk-values, which correspond directly to barrer units (=10-11cm2 ml O2/sec ml mmHg).
Karlen, T., Ludi, A., Mühlebach, A., Bernhard, P., Pharisa, C., (1995) J. Polym. sci. Polym. Chem. Ed. 33, 1665.
In fact, the addition of a crystal of [Ru(H2O)6]tos2 (C1) to liquid 4-methyl-l 1-oxatricyclo [6.2.1.02,7]undeca-2,4,6,9-tetraene (M7) led to an immediate explosion
Hafner, A., Mühlebach, A., van der Schaaf, P. (1997) Angew. Chem. 109, 2213 and (1997) Angew. Chem. Int. Ed. Engl. 36, 2121.
Catalyst C3 (R=cyclohexyl) even allows aqueous dispersion polymerization of NBE and DCPD: see second paper of Mühlebach, A. et al. (NATO-ASI Series)
Mühlebach, A, Van der Schaaf, P.A., Hafner, A., Setiabudi, F. (1998) J. Mol. Catal. 132, 181.
Mühlebach, A., Schaedeli, U, Bernhard, P. (1994) Polym. Prepr. 35, 963. Mühlebach, A., Schaedeli, U. (1996) ACS Symp. Series 620, p. 364.
Masuda, T., Iguchi, Y., Tang, B.-Z., Higashimura, T. (1988) Polymer 29, 2041.
Masuda, T., Kawasaki, M., Okano, Y., Higashimura, T. (1982) Polymer Journal 14, 371.
Van der Schaaf, P.A., Hafner, A., Mühlebach, A. (1996) Angew. Chem. 108, 1974; (1996) Angew. Chem., Int. Ed. Engl. 35, 1845; Hafner, A.; Van der Schaaf, P.A.; Mühlebach, A. (1996) Chimia 50, 131.
Schrock, R.R. (1990) Acc. Chem. Res. 23, 158.
Savoca, A.C., Surnamer, A.D.; Tien, C. (1993) Macromolecules 26, 6211.
Van der Schaaf, P.A., Hafner, A., Mühlebach, A. EP 799, 266.
Schrock R.R. et al. (1990) J. Am. Chem. Soc. 112, 3875.
P.A. van der Schaaf, P.A., Hafner, A., Mühlebach, A. (1996) Angew. Chem. 108, 1974.
Van der Schaaf, P.A., Grove, D.M., Smeets, W.J.J., Spek, A.L., Van Koten, G. (1993) Organometallics 12, 3955
Osram HBO 200 W/2, Spindler & Hoyer, D-Göttingen.
Recently, linear poly(DCPD) was synthesized using catalytic systems derived from WCl6 and WOCl4 and organosilicon compounds: Abadie, M.J., Dimonie, M., Couve, C., Dragutan, V. (2000) European Polymer Journal 36, 1213. The polymer had prevailingly cis double bond configuration and showed a Tg of 53°C (measured by DSC).
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. (2002). New Materials from Thermal and Photoinduced Ring Opening Metathesis Polymerisation (ROMP/PROMP). 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_10
Download citation
DOI: https://doi.org/10.1007/978-94-010-0373-5_10
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-0559-6
Online ISBN: 978-94-010-0373-5
eBook Packages: Springer Book Archive