Structural control during the cyclopolymerization of unconjugated dienes

Kodaira, Toshiyuki

doi:10.1016/s0079-6700(00)00016-2

Cited by 62 publications

(60 citation statements)

References 94 publications

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“…The inhibiting effect (referred to above) on the polymerization rate of the less electron‐withdrawing phosphonic acid group in monomer 5 overcomes the enhancing steric effect due to its smaller size with respect to the phosphonate ester group in monomer 2. Low polymerizability of monomer 7 (containing 40 mol‐% of monomer 1), the monofunctional counterpart of monomer 1, supports the principle proposed by Kodaira 21…”

Section: Resultssupporting

confidence: 79%

“…We can attempt to predict the polymerization behavior of our monomers based on the studies done by Kodaira and Mathias et al,17, 21, 22 in which it is proposed that unconjugated dienes with both a high cyclization tendency and a high polymerizability can be obtained by the use of functional groups with no homopolymerization tendency along with a highly conjugative nature. For example 1,6‐heptadienes with conjugated CC and CO bonds from α ‐substituted acrylates will have high polymerizabilities even though their monofunctional counterparts do not polymerize due to steric effects 21. The steric effects will inhibit the intermolecular propagation reaction to favor intramolecular reaction and will therefore give rise to highly cyclized polymers.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Influence of Structure on Polymerization Rates and Ca‐Binding of Phosphorus‐Containing 1,6‐Dienes

Albayrak¹,

Bilgici²,

Avcı³

2007

Macro Reaction Engineering

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Photo‐ and thermal‐polymerizations of 4‐diethoxyphosphoryl‐2,4,6‐tris(ethoxycarbonyl)‐1,6‐heptadiene, 4,4‐bis(diethoxyphosphoryl)‐2,6‐bis(t‐butoxycarbonyl)‐1,6‐heptadiene and 4‐diethoxyphosphoryl‐4‐ethoxycarbonyl‐2,6‐bis(t‐butoxycarbonyl)‐1,6‐heptadiene monomers and their phosphonic and carboxylic acid derivatives were investigated to understand the effect of the cyclic monomer structure on their polymerization reactivity. A strong effect of the substituents at positions 2, 4 and 6 of the monomers on polymerization rate was observed. The polymerizability of the monomers was successfully correlated with the 13C NMR chemical shifts of the vinyl carbons. Conversion values were consistent with the Tg being a measure of the flexibility of a monomer. The monomers containing phosphonic acid groups were soluble in water and ethanol. The acidic nature of the aqueous solutions of these monomers is expected to give them etching properties, important for dental applications. The interaction of the acid monomers with hydroxyapatite was investigated using 13C NMR technique.

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Section: Resultssupporting

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Influence of Structure on Polymerization Rates and Ca‐Binding of Phosphorus‐Containing 1,6‐Dienes

Albayrak¹,

Bilgici²,

Avcı³

2007

Macro Reaction Engineering

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“…Cyclopolymerization [23][24][25][26][27][28][29][30][31][32][33][34][35][36] is a chain polymerization of bifunctional monomers via alternating propagation process of intramolecular cyclization and intermolecular addition, to give soluble linear polymers consisting of 'in-chain' cyclic structures. This strategy affords direct and quantitative incorporation of cyclic units into polymers as repeating units, in sharp contrast to the polymerization of monomers bearing a cyclic pendent group 37 or the postfunctionalization of linear polymers 38 .…”

mentioning

confidence: 99%

Polymeric pseudo-crown ether for cation recognition via cation template-assisted cyclopolymerization

et al. 2013

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Cyclopolymerization is a chain polymerization of bifunctional monomers via alternating processes of intramolecular cyclization and intermolecular addition, to give soluble linear polymers consisting of in-chain cyclic structures. Though cyclopolymers comprising in-chain multiple large rings potentially show unique functionality, they generally require the elaborate design of bifunctional monomers. Here we report cation template-assisted cyclopolymerization of poly(ethylene glycol) dimethacrylates as an efficient strategy directly yielding polymeric pseudo-crown ethers with large in-chain cavities (up to 30-membered rings) for selective molecular recognition. The key is to select a size-fit metal cation for the spacer unit of the divinyl monomers to form a pseudo-cyclic conformation, where the two vinyl groups are suitably positioned for intramolecular cyclization. The marriage of supramolecular chemistry and polymer chemistry affords efficient, one-pot chemical transformation from common chemical reagents with simple templates to functional cyclopolymers.

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“…soluble linear polymers comprising consecutive in-chain rings ( Figure 4c) (33)(34)(35)(36)(37)(38)(39)(40). Selective cyclopolymerization without gelation involves efficient intramolecular cyclization of divinyl monomers so as to incorporate both of the two olefins into a main chain without dangling olefins in polymers.…”

Section: Figure 4 Polymerization Of Divinyl Compounds: (A) Gelation;mentioning

confidence: 99%

Sequence-Regulated Polymers via Living Radical Polymerization: From Design to Properties and Functions

Terashima

Sawamoto

2014

ACS Symposium Series

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Sequence-regulated polymers have been recently designed and synthesized via ruthenium-catalyzed living radical polymerization for unique physical properties and functions. This chapter summarizes the recent advances on the following topics: 1) gradient copolymers via concurrent tandem catalysis of living radical polymerization and in situ transesterification of methacrylates with alcohols; 2) cyclopolymers comprising in-chain large poly(ethylene glycol) (PEG) rings via cation template-assisted cyclopolymerization of PEG dimethacrylates for cation recognition; 3) single-chain folding of amphiphilic random copolymers into compact unimer micelles in water with intramolecular hydrophobic interaction.

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Structural control during the cyclopolymerization of unconjugated dienes

Cited by 62 publications

References 94 publications

Influence of Structure on Polymerization Rates and Ca‐Binding of Phosphorus‐Containing 1,6‐Dienes

Influence of Structure on Polymerization Rates and Ca‐Binding of Phosphorus‐Containing 1,6‐Dienes

Polymeric pseudo-crown ether for cation recognition via cation template-assisted cyclopolymerization

Sequence-Regulated Polymers via Living Radical Polymerization: From Design to Properties and Functions

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