Polymerizations organometallic monomers

Two major approaches to the formation of materials of this type have involved the derivatization of preformed organic polymers with organometallic functions and the synthesis and polymerization of organometallic monomers that contain vinyl substituents For the transition metals, condensation polymerizations have also been investigated. However, the reactions have generally been conducted at elevated temperatures, and the resulting products have often not... 

Only a few examples of the cationic polymerization reactions of organometallic monomers have been reported in the literature. 

Organometallic compounds containing polymerizable carbon-carbon double bonds have been synthesized and their polymerization studied [Archer, 2001 Pittman et al., 1987]. Among the organometallic monomers studied are vinylferrrocene and trialkyltin methacrylate. Much of the interest in these polymerizations has been to obtain polymers with... 

Kuran, W., Polar Vinyl Monomer Polymerization and Copolymerization with Olefins Promoted by Organometallic Catalysts , Polimery, 42, 604-609 (1997). 

Addition polymerization of ferrocene-containing vinyl monomers is probably the earliest preparation method that has been widely studied. Vinylferrocene 1 [5], the first organometallic monomer, was synthesized in 1955 and its polymerization behavior has been extensively studied under radical [5, 6], cationic [7], and Ziegler-Natta conditions [7] it is inert to anionic initiation [8]. 

Since the yield in the oxidative coupling is practically quantitative, the oxidative polymerization of a,( )-diethynyl monomers would be expected to yield high molecular weight, linear polymers, as shown in equation (18). Hay has reported that almost any diethynyl monomer, even organometallic monomers, can be polymerized to high molecular weight polymers in Ae presence of a soluble amine complex catalyst of a copper(I) salt (Hay modification). ... 

A new general route to a large variety of T)5-(vinylcyclopentadienyl) organometallic monomers was achieved in cooperation with Rausch.46,54,57,76 The lithium salts of vinylcy-clopentadienide and isopropenylcyclopentadienide were prepared (respectively), from which a large variety of new monomers, including 2-18 and 24-30 and 39 were generated (see Schemes 1.3 and 1.4). This led to many polymerizations a few are mentioned here. 

In this paper we review the recent work on plasma polymerization of organometallic monomers and discuss the room temperature... 

Attempts to conduct a cationic polymerization of these MCMs (BF3 as the catalyst) have not been successful, apparently because of the interaction of the palladium MCM with BF3. Moreover, the polymerization of organometallic monomers can be complicated by a whole series of side-reactions. 

Insertion polymerization is usually catalyzed by an organometallic compound and a monomer is inserted between the metal ion and the carbon atom adjacent to the metal (carboanion). As a result, the polymer chain is pushed out from the solid catalyst surface. Usually, addition polymerizations are involved in the polymerization of olefinic monomers. Polymerization occurs via an insertion of a monomer at the end of the growing chain, mediated by a catalyst. The catalyst stays at the end of the growing chain. Polymers synthesized by insertion polymerization are typically characterized by a very high stereo-regularity. An example of such a polymerization technique is the Ziegler-Natta-catalyzed polymerization. 

NEW VINYL ORGANOMETALLIC MONOMERS SYNTHESIS AND POLYMERIZATION BEHAVIOR... 

All of these interesting features of the model organometallic monomer raised questions about other n -vinylcyclopentadienyl-transition metal monomers. Could they be synthesized, polymerized, or copolymerized To that end, (n -vinylcyclopentadienyl)tricarbonyl-manganese, 4.(q vinylcyclopentadienyl)dicarbonylnitrosyl-chromium, and 3—vinvl bis f nival anadi iron. war a nr ana... 

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