Polymers methyllithium

The monomer 19 can also be polymerized using analogous methods of initiation to those employed in organic polymer science. Radical initiators afford regioirregular polymers, whereas anionic initiators add selectively to the phosphorus atom of the P=C bond and thus yield a regioregular polymer [85]. The product of the initial addition of MeLi across the P=C bond, Mes(Me)P-CPh2Li, was identified spectroscopically. The polymers obtained from anionic initiation are spectroscopically identical to those obtained from the thermolysis. Reasonable molecular weights (ca. 5000-10,000 g mol 0 are obtained when methyllithium is used as an initiator. 

We have examined the influence of diphenyl ether and anisole on the association of the polystyryllithium and the 1,1-diphenyl-methyllithium active centers in benzene solution. The analytical tool used was the vacuum viscometry method (1 .2. 2. ) which utilizes concentrated solutions of polystyryllithium and the terminated polymer in the entanglement regime. Our results show that the presence of these ethers can alter the association states of the foregoing active centers. These findings parallel previous work (2) involving tetrahydrofuran. 

Although benzyllithium has been aminated to 97% yield using these reagents- attempted amination of poly(styryl)lithium (IVI = 2 x 10 ) was achieved with only 5 % efficiency using literature procedures After extensive modification of those procedures, poly(styryl)Iithium has been aminated with 92% efficiency using a twofold excess of methoxyamine/methyllithium . In addition, pure 1 ° amine-terminated polystyrene can be isolated by silica gel chromatography since it is easily separated from the unaminated polymer. 

The functionalization of polymeric organolithium compounds with 3,4-epoxy-1-butene (EPB) provides the potential to prepare a polymer molecule with dual functionality as well as a potential precursor to a diene-functionalized macromonomer. It has been shown that the reaction of EPB with methyllithium results in three modes of addition to the... 

However, these polymers were found to be very poor conductors, even after doping with iodine. Another type of acetylenic polymer, poly(silylenediethynylene), (SiR2C=C—C ),j (10), can be synthesized by condensation of Cl2SiR R (R, R = CH3, C2H5, or CeHs) and l,4-dilithio-l,3-butadiyne prepared from 1,4-bistrimethylsilylbut-l,3-diyne and methyllithium (eq. 10) (75). 

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