Living polymers ring opening metathesis polymerization

Besides the polymerization techniques discussed above, other polymerization methods have been used for the preparation of surface grafts. Recently, ring-opening metathesis polymerization (ROMP) became popular. This polymerization type will be discussed by Buchmeiser in Chapter 8. Recently, interesting accounts have appeared on solventiess polymerization techniques applying (living) ROMP on surfaces to prepare structured brush surfaces of conjugated polymers [331, 332]. 

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. 

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

Figure 7.12 Ring-opened metathesis polymerization (ROMP) of cyclooctene. Note that ROMP could be initiated with any M=CR2, and for a living polymer the end group will be CH=CR2.

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. 

Ring-opening metathesis polymerization provides a platform on which to create living polymers with varied biologically active functionalities.These polymers have been used both for antimicrobial and cell-penetrating peptide mimic purposes. The first class of ROMP polymers made used an imide-functionalized oxanorbornene structure. llker... 

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