Synthesis of soluble poly(divinylbenzene‐<i>co</i>‐styrene) and poly(divinylbenzene‐co‐vinylpyridine) by lithium amide‐initiated anionic copolymerization

Nagasaki, Yukio; Taniuchi, Masahiro; Tsuruta, Teiji

doi:10.1002/macp.1988.021890402

Cited by 12 publications

(4 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 1978, Tsuruta et al reported a particular and exceptional case where soluble polymers were obtained in high yields (∼90%) by the anionic polymerization of 1 with lithium diisopropylamide in the presence of an excess of diisopropylamine. − This is probably due to the stabilization of the propagating chain-end anion by weak interaction with excess amines and the stabilized chain-end anion may possibly add to the pendant vinyl group much more slowly than the vinyl polymerization of 1 . However, the resulting polymers were observed to possess broad multimodal molecular weight distributions, indicating that they were highly branched in structure.…”

Section: Introductionmentioning

confidence: 99%

Living Anionic Polymerization of 1,4-Divinylbenzene and Its Isomers

et al. 2012

View full text Add to dashboard Cite

The anionic polymerization of 1,4-divinylbenzene (1) and its ortho (2) and meta isomers (3) were studied under a variety of conditions. One of the two vinyl groups of 1 was selectively and exclusively polymerized in a living manner by the addition of a suitable additive under the conditions of −78 °C for 1 min and −95 °C for 30 min. Under such conditions, the unwanted addition reaction of the chain-end anion to the pendant vinyl group was almost suppressed and soluble polymers with predictable molecular weights of up to 60 500 g/mol and narrow molecular weight distributions (M w/M n < 1.05) were quantitatively obtained. The amount of dimerized chain produced by the addition reaction was negligible or very small (<5%). The effective additives in the polymerization involve potassium alkoxides and phenoxides, derived from tert-butyl alcohol, sec-butyl alcohol, 2,4-dimethyl-3-pentanol, 1-methylcyclohexanol, 1:2,5:6-di-O-isopropylidene-α-d-glucofuranose, phenol, 1-naphthol, and 2,6-di(tert-butyl)-4-methylphenol, and potassium carboxylate derived from pivalic acid. The living polymer of 1 was not stable at −78 °C after 5 min or longer times, but very stable at −95 °C even for 30 min. The chain-end anion could be stabilized by end-capping with tert-butyl methacrylate and 1,1-diphenylethylene, and the resulting anions remained unchanged at −78 °C even after several hours.

show abstract

Section: Introductionmentioning

confidence: 99%

Living Anionic Polymerization of 1,4-Divinylbenzene and Its Isomers

et al. 2012

View full text Add to dashboard Cite

show abstract

“…Interestingly, soluble polymers were obtained in the anionic polymerizations of 1,3-and 1,4-divinylbenzenes with use of lithium diisopropylamide in the presence of diisopropylamine. [10] This polymerization was however not a living system. In contrast to these results, the anionic polymerization of isopropenylbenzenes can be controlled to some extent.…”

Section: Introductionmentioning

confidence: 99%

Living Anionic Polymerization of Functionalized Monomers, 2. Anionic Polymerization ofp-Alkenylstyrene Derivatives

Hirao¹,

Kubota

Sueyoshi

et al. 2001

Macromol. Chem. Phys.

View full text Add to dashboard Cite

“…A particular case was reported by Tsuruta, Nagasaki, and their co-workers where soluble polymers were obtained in high yields (∼90%) by the anionic polymerization of 1 with lithium diisopropylamide with an excess of diisopropylamine. − The authors suggested that the excess diisopropylamine would play an important role in stabilizing the chain-end carbanion enough to become inactive toward the pendant double bond. However, termination reactions between the excess diisopropylamine and the chain-end anion often occurred during polymerization and, therefore, this system was far from living polymerization.…”

mentioning

confidence: 99%

Living Anionic Polymerization of 1,4-Divinylbenzene

et al. 2011

View full text Add to dashboard Cite

I n usual vinyl polymerization, 1,4-divinylbenzene (1) and its isomers are widely used as cross-linking agents. In fact, the radical or anionic copolymerization of 1 with other vinyl monomer(s) generally leads to gel formation at an early stage of polymerization, giving cross-linked materials insoluble in all solvents. These cross-linked materials are often utilized as various ion-exchange resins and reactive micro-and macro-gels. By reacting living anionic polymers of styrene, 1,3-butadiene, or isoprene with 1, many-armed star-branched polymers are readily prepared via addition reaction followed by cross-linking reactions. 1 Surprisingly, soluble lightly branched polymers having a pendant vinyl group can be obtained under appropriate conditions in the anionic polymerization of 1 or the anionic copolymerization of 1 and styrene or 1,3-diene monomers. 2À11 The formation of a soluble polymer is undoubtedly attributed to the fact that the pendant vinyl group in the polymer chain is much lower in reactivity than the vinyl group(s) in 1 activated by a long conjugation system ranging from the vinyl group to the other one via the phenyl group. Accordingly, the initiation, followed by the propagation reaction, may precede the pendant vinyl group attack by the chain-end anion leading to the cross-linking. Different reactivity between the vinyl groups in 1 and the pendant one is indicated by kinetic studies of the polymerization of 1 and 1 H NMR analysis of the resulting polymers and model compounds 2À4,10À12 However, cross-linking among polymers usually occurs at the final stage of the polymerization to result in insoluble polymers even in such polymerizations.A particular case was reported by Tsuruta, Nagasaki, and their co-workers where soluble polymers were obtained in high yields (∼90%) by the anionic polymerization of 1 with lithium diisopropylamide with an excess of diisopropylamine. 12À16 The dx.

show abstract

Synthesis of soluble poly(divinylbenzene‐co‐styrene) and poly(divinylbenzene‐co‐vinylpyridine) by lithium amide‐initiated anionic copolymerization

Cited by 12 publications

References 12 publications

Living Anionic Polymerization of 1,4-Divinylbenzene and Its Isomers

Living Anionic Polymerization of 1,4-Divinylbenzene and Its Isomers

Living Anionic Polymerization of Functionalized Monomers, 2. Anionic Polymerization ofp-Alkenylstyrene Derivatives

Living Anionic Polymerization of 1,4-Divinylbenzene

Contact Info

Product

Resources

About