Ring-opening metathesis polymerization ROMP polymers

Y. Xia and R. C. Larock, Castor oil-based thermosets with varied crosslink densities prepared by ring-opening metathesis polymerization (ROMP) , Polymer, 2010,51,2508-14. 

Xu W, Chung Ch, Kwon Y (2007) Synthesis of novel block copolymers containing polyhedral oligomeric sUsesquioxane (POSS) pendent groups via ring-opening metathesis polymerization (ROMP). Polymer 48 6286-6293... 

Aqueous ring-opening metathesis polymerization (ROMP) was first described in 1989 (90) and it has been appHed to maleic anhydride (91). Furan [110-00-9] reacts in a Diels-Alder reaction with maleic anhydride to give exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3—dicarboxylate anhydride [6118-51 -0] (24). The condensed product is treated with a soluble mthenium(Ill) [7440-18-8] catalyst in water to give upon acidification the polymer (25). Several apphcations for this new copolymer have been suggested (91). 

A drawback to the Durham method for the synthesis of polyacetylene is the necessity of elimination of a relatively large molecule during conversion. This can be overcome by the inclusion of strained rings into the precursor polymer stmcture. This technique was developed in the investigation of the ring-opening metathesis polymerization (ROMP) of benzvalene as shown in equation 3 (31). 

Wolfe and Wagener have developed main-chain boronate polymers (59) (Fig. 38) by the acyclic diene metathesis (ADMET) polymerization of symmetrical ,oj-dienes, containing both methyl- and phenyl-substituted boronate functionalities using Mo and Ru catalysts.84 The ring-opening metathesis polymerization (ROMP) of several norbornene monomers containing methyl- and phenyl-substituted boronates into... 

Fig.4A,B. Ring-opening metathesis polymerization (ROMP) A Structures of organometal-lic initiators that have been used in ROMP to generate neobiopolymers. B General pathway for polymer synthesis using ROMP. Molybdenum-initiated reactions are typically capped with aldehydes and ruthenium-initiated with end ethers.

See also ROM polymers Ring-opening metathesis polymerization (ROMP) reaction, 20 413 Ring-opening polymerization (ROP), 24 271, 29 816-817, 23 702,... 

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]. 

Olefin metathesis (olefin disproportionation) is the reaction of two alkenes in which the redistribution of the olelinic bonds takes place with the aid of transition metal catalysts (Scheme 7.7). The reaction proceeds with an intermediate formation of a metallacyclobutene. This may either break down to provide two new olefins, or open up to generate a metal alkylidene species which -by multiple alkene insertion- may lead to formation of alkylidenes with a polymeric moiety [21]. Ring-opening metathesis polymerization (ROMP) is the reaction of cyclic olefins in which backbone-unsaturated polymers are obtained. The driving force of this process is obviously in the relief of the ring strain of the monomers. 

Another two polymers, which have been used for the same type of arene-catalyzed lithiation reactions, are compounds 596 and 597, which were prepared by ring-opening metathesis polymerization (ROMP) starting from the corresponding aryl norbonenes 598. ... 

The polymerization of cyclic, strained olefins by transition metal alkylidenes of general formula L M = CRR (L = ligand, R, R = H, alkyl, aryl) yields polymers formed via ring-opening that contain unsaturated double bonds within each repetitive unit. Since the mechanism is based on repetitive metathesis steps, this polymerization reaction is known as ring-opening metathesis polymerization (ROMP) (Scheme 1). 

Polymers using the ring opening metathesis polymerization (ROMP) technique were first obtained at 1960 by Eleuterio (1,2). The patents deal with the polymerization of bicyclo[2.2.1]heptene-2, i.e., nor-bomene using a molybdenum catalyst dispersed on alumina. 

M.R. Buchmeiser, F. Sinner, M. Mupa, and K. Wurst, Ring-opening metathesis polymerization (ROMP) for the preparation of surface-grafted polymer supports, Macromolecules, 33(l) 32-39, January 2000. 

Basically, COCs can be manufactured by ring opening metathesis polymerization (ROMP) as described in the chapter about metathesis polymers. However, ROMP offers disadvantages as main chain double bonds must be hydrated after polymerization. Therefore, COCs are more conveniently straightforwardly prepared by addition polymerization. 

The ring-opening metathesis polymerization (ROMP) of cyclic alkenes yields polymers that still contain all double bonds [Eq. (13)]. 

Remarkable development over the last 10-15 years in the synthesis of well-defined functional-group-tolerant ruthenium carbenes (Grubbs-related catalysts) also caused real development of the metathesis-based reactions in organosilicon polymers. For recent reviews on metathesis of organosilicon compounds see Refs. [6,7]. Unsaturated organosilicon polymers can be synthesized via ruthenium carbene catalyzed ring-opening metathesis polymerization (ROMP) of silylsubstituted cycloalkenes (Eq. 113). 

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