Polymerization of olefins anionic

On the other hand, monomers like acrylic or methacrylic esters and conjugated dienes require strong bases, like alkali metals or organometallic compounds. 

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Bywater, S., Anionic Polymerization of Olefins, Chap. 1 in Comprehensive Chemical Kinetics, Vol. 15, Non-Radical Polymerization, C. H. Bamford and C. F. H. Tipper, eds., Elsevier, New York, 1976. 

Bywater, S., Anionic Polymerization of Olefins, Chap. 1 in Comprehensive Chemical Kinetics, Vol. 15,... 

Boron alkyls are expected to be inactive for coordinated anionic polymerization of olefins because the boron-carbon bond is not sufficiently ionic. The diazomethane polymerization with boron alkyl catalyst reported by Bawn, Ledwith and Matthies (275) is a special case of the growth reaction. A coordination mechanism seems most probable, but it has not been ascertained whether the polymer chain migrates as a car-banion or as a radical. If the complex between diazomethane and boron decomposes into a boron-carbene complex, then the polymer chain could migrate as a carbanion with the driving force provided by the electrophilic carbonium ion ... 

Catalysts of the Ziegler-Natta type are applied widely to the anionic polymerization of olefins and dienes. Polar monomers deactivate the system and cannot be copolymerized with olefins. J. L. Jezl and coworkers discovered that the living chains from an anionic polymerization can be converted to free radicals by the reaction with organic peroxides and thus permit the formation of block copolymers with polar vinyl monomers. In this novel technique of combined anionic-free radical polymerization, they are able to produce block copolymers of most olefins, such as alkylene, propylene, styrene, or butadiene with polar vinyl monomers, such as acrylonitrile or vinyl pyridine. 

An unusual application of Equation (3.1) was made in a study of anionic polymerization of olefins as a function of the olefin and of the initiator, AB. ... 

Although numerous mechanism proposals have been offered for the coordinated anionic polymerization of olefins, no direct proof exists to confirm the proposed structures. Although the structures have value in stimulating future research to verify certain features of the mechanism, noncritical acceptance of the proposal as fact could hinder progress. 

Bywater S. Anionic polymerization of olefins. In Bamford CH, Tipper CFH, editors. Comprehensive Chemical Kinetics. Volume 15. New York Elsevier 1976. p 1. 

Amides induce anionic polymerization of olefins like styrene, methyl methacrylate, acrylonitrile [5], cyclohexenone [6], and ethylene oxide [7] in solution. The amination of ethene and propene by NH3 in the gas phase or in NH3 solution is catalyzed by amides [8]. 

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