Living anionic stereospecific polymerization of 2‐vinylpyridine, 2. Kinetics of polymerization and nature of active centres

Soum, Alain; Fontanille, Michel

doi:10.1002/macp.1981.021820615

Cited by 22 publications

(7 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Until the 1960s only radical poylmerization of 2-vinylpyridine (2VP) to atactic P2VP was possible. [28][29][30][31] Apart from the mentioned examples only few groups investigated the stereospecific polymerization of 2VP. 26,27 They were able to obtain isotactic P2VP with magnesium amides.…”

mentioning

confidence: 99%

Stereospecific catalytic precision polymerization of 2-vinylpyridine via rare earth metal-mediated group transfer polymerization with 2-methoxyethylamino-bis(phenolate)-yttrium complexes

et al. 2015

View full text Add to dashboard Cite

2-Methoxyethylamino-bis(phenolate)-yttrium complexes were employed in the catalytic precision polymerization of 2-vinylpyridine (2VP). The C 1 -symmetric catalyst systems are able to isospecifically polymerize prochiral 2-vinylpyridine with moderate to high activities. Tacticities ranging from atactic to isotactic can be achieved (P m = 0.54-0.74). Mechanistic studies through 13 C NMR microstructure analysis of the resulting isotactic P2VP show an enantiomorphic site control mechanism.

show abstract

mentioning

confidence: 99%

Stereospecific catalytic precision polymerization of 2-vinylpyridine via rare earth metal-mediated group transfer polymerization with 2-methoxyethylamino-bis(phenolate)-yttrium complexes

et al. 2015

View full text Add to dashboard Cite

show abstract

“…2-Vinylpyridine readily undergoes living anionic polymerization in THF at −78 • C with π-stabilized bulky initiators, such as 1,1-diphenylhexyllithium, 1,1-diphenyl-3-penyllithium, Ph 2 CHLi, and even Grignard reagents [1,2,33,64,65]. 2-Vinylpyridine readily undergoes living anionic polymerization in THF at −78 • C with π-stabilized bulky initiators, such as 1,1-diphenylhexyllithium, 1,1-diphenyl-3-penyllithium, Ph 2 CHLi, and even Grignard reagents [1,2,33,64,65].…”

Section: -And 4-vinylpyridinesmentioning

confidence: 99%

Anionic Polymerization: Recent Advances

Ishizone

Hirao

2012

Materials Science and Technology

View full text Add to dashboard Cite

polymerize the monomers in classes B, C, and D, but they cannot initiate the polymerization of monomers in class A. The initiators in class c can polymerize both C and D class monomers, while they are inert for the monomers in classes A and B. The least-reactive initiators in class d, such as amines and phosphines, undergo anionic polymerization of the most-reactive D class monomers Among the monomers, α-cyanoacrylate is polymerized, even with water.The relationship between a monomer and its growing chain-end anion is also important in order to understand anionic polymerization behavior. In general, the most-reactive chain-end anions derive from the least-reactive monomers and vice-versa, because they are conjugated bases and acids with each other. For example, when considering styrene (class A) and methyl methacrylate (MMA) (class B), the latter is more reactive than the former because the electron density on the C=C bond of MMA is considerably reduced by the electron-withdrawing ester carbonyl group, whereas that on the styrene C=C bond is influenced much less by the phenyl group. On the other hand, the chain-end anion derived from MMA is also reduced in electron density by the same electron-withdrawing effect, and becomes less reactive than that derived from styrene. In practice, the chain-end anion from MMA has no ability to polymerize styrene, whilst the chain-end anion from styrene can polymerize styrene and, of course, the more-reactive MMA. Thus, the monomers in class A will always produce the most reactive growing chain-end anions that can polymerize all monomers in classes A, B, C, and D. In contrast, the least-reactive chain-end anions derived from the most-reactive monomers in class D can polymerize only the monomers in class D. These relationships are very important -even critical -for selecting the correct anionic initiator in polymerization, as well as when synthesizing block copolymers.

show abstract

“…Solvent ( These results differ considerably from those obtained for the polymerization of 3 under comparable conditions -13). In these cases, predominantly isotactic products were obtained, and this has been attributed to intramolecular coordination of the counter ion with the penultimate pyridine nitrogen2, 14). The statistics of this polymerization, moreover, appear to be non-Bernoullian.…”

Section: Run Cationmentioning

confidence: 99%