Living ring-opening metathesis polymerization

Ring-Opening Metathesis Polymerization. Several new titanacyclobutanes have been shown to initiate living ring-opening metathesis polymerization (ROMP) systems. These have been used to make diblock and triblock copolymers of norbomene [498-66-8] (N) and its derivatives (eg, dicyclopentadiene [77-73-6] (D)) (Fig. 2) (41). 

Dalphond J, Bazzi H, Kahrim K, Sleiman H. Synthesis and self-assembly of polymers containing dicarboximide groups by living ring-opening metathesis polymerization. Macromol Chem Phys 2002 203 1988-1994. 

Black, G. Maher, D. Risse, W. Living Ring-opening Metathesis Polymerization. In Handbook of Metathesis, Grubbs, R. H., Ed. Wiley-VCH Weinheim, 2003 Vol. 3, pp 2-71. 

Living ring opening metathesis polymerization is a special kind of ROMP. In order to approach the conditions of a living polymerization reaction, the following requirements must be fulfilled (12) ... 

C.W. Bielawski and R.H. Grubbs, Living ring-opening metathesis polymerization, Prog. Polym. Sci., 32(1) 1—29, January 2007. 

G. Black, D. Maher, and W. Risse, Living Ring-Opening Metathesis Polymerization, in Handbook of Metathesis, Vol. 3, R. H. Grubbs, Ed., Wiley-VCH Weinheim, Germany, 2003, p. 20. 

Matyjaszewski et al. demonstrated that living ring opening metathesis polymerization (ROMP) could also be combined with ATRP to produce novel block copolymers [292]. ROMP of norbornene (NB) and dicyclopentadiene (CPD) were performed using an Mo-alkylidene complex, followed by reaction with p-(bro-momethyl) benzaldehyde to generate a benzyl bromide terminated polymer capable of being used as a macroinitiator for ATRP (Scheme 41). 

The development of living ring-opening metathesis polymerization (ROMP cf. Section 6.10) catalysts was greatly influenced by the initial use of hydrated late transition metal salts. In the aqueous polymerization of 7-oxanorbornene derivatives, RuC13 and [Ru(H20)6]2+ were found to produce polymer with the latter having a smaller induction period [68], A key intermediate and product in the reaction is the alkene adduct, [Ru(H20)5(alkene)]2+ with the use of RuC13 and... 

Living ring opening metathesis polymerization methods (ROMP) were first employed to synthesize LC-coil diblock copolymers by Komiya and Shrock [80] in 1993. The structure of their polymer system is shown in Scheme 7D. Recent work from Grubbs group also used a novel ruthenium catalyst which can tolerate more functional groups [81] to synthesize well-defined LC-coil block copolymers [82]. The ROMP polymer backbone can be hydrogenated to create saturated structure to improve its stability. 

Percec, V. Schlueter. D. Mechanistic investigations on the formation of supramolecular cylindrical shaped oligomers and polymers by living ring opening metathesis polymerization of a 7-oxanorbornene monomer substituted with two tapered monodendrons. Macromolecules 4997. 30. 5783. 

Wang, Y.C., Li, C.L., Lee, K.R. and Liaw, D.J. 2005. Pervaporation separation of aqueous alcohol solution through a carbazole-functionalized norbornenederivative membrane using living ring-opening metathesis polymerization. J Memh S l. 246 59-65. 

Schrock, R. R. Living Ring-Opening Metathesis Polymerization Catalyzed by Well-Characterized Transition-Metal Alkylidene Complexes. Accounts of Chemical Research, 1990,23,158-165. 

Living Ring-Opening Metathesis Polymerization (LROMP)... 

Schrock, R. R. Living ring-opening metathesis polymerization catalyzed by well-characterized transition metal alkylidene complexes. Acc. Chem. Res. 1990, 23, 158-165. 

Gratt J, Cohen RE (1997) Synthesis of block copolymers containing pendant carbazole groups via living ring-opening metathesis polymerization. Macromolecules 30 3137-3140... 

Albagli, D., G. Bazan, M. S. Wrighton, and R. R. Schrock. 1992. Well-defined redox-active polymers and block copolymers prepared by living ring-opening metathesis polymerization. (11) 4150 158. 

Titanacyclobutanes, catalysts for living ring opening metathesis polymerization (ROMP) of strained cyclic olefins, have been transformed into Ziegler-Natta catalysts. The synthetic routes that allow the transformation of 3,3-dimethylcyclopropene-titanacyclobutane 1, the most effective initiator of these ROMP polymerizations, and of trisubstituted titanacycles, such as 3, into the corresponding chlorine or ethoxy derivatives are... 

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