Novel Template Polymerization via Radical Ring-Opening Isomerization. 1. Polymerization of 4-Methylene-1,3-dioxolane on the Polymer Side Chain

Sugiyama, Jun-ichi; Yokozawa, Tsutomu; Endo, Takeshi

doi:10.1021/ma00086a001

Cited by 6 publications

(4 citation statements)

References 3 publications

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“…When the concentration of free radical initiator is very low, polymerization might not progress efficiently. The results of runs [11][12][13][14] showed that all K % values were higher than the K % value in run 18 in which homopolymer 1 was used. Therefore suitable dilution of the local concentration by comonomer around a 1:1 molar ratio was found to lead to good separation between the newborn and the template polymer.…”

Section: Resultsmentioning

confidence: 99%

“…[2][3][4][5][6][7][8][9][10][11] In particular, 2,2-diphenyl-4-methylene-1,3-dioxolane is interesting because it undergoes quantitative elimination polymerization to afford poly-(oxotrimethylene) with equimolar benzophenone by radical initiation.12 Recently, we have applied this reaction to novel template polymerization and achieved radical elimination polymerization of polyfunctional macromonomer 1 on its side chain (Scheme l). 13 The obtained postpolymer 2 was divided into two parts by fractional precipitation without postchemical treatment. The DMF soluble part abounded with template polymer T, and the DMF insoluble part abounded with newborn polymer N, correspondingly.…”

Section: Introductionmentioning

confidence: 99%

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Novel Template Polymerization via Radical Ring-Opening Isomerization. 2. Polymerization of Copolymer Obtained from 4-Methylene-2-phenyl-2-(4-vinylphenyl)-1,3-dioxolanes with Styrene

Sugiyama¹,

Yokozawa²,

Endo³

1994

Macromolecules

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Simultaneous separating template polymerizations of copolymers 4a and 4b obtained from 4-methylene-2-phenyl-2-(4-vinylphenyl)-l,3-dioxolanes with styrene were carried out. Polymerizable functional groups on the side chain of 4 underwent chain reaction with a free radical initiator to afford poly-(oxotrimethylene) as a newborn polymer 7N accompanying release of copoly(vinylbenzophenone/styrene) as a template polymer 7T. The postpolymers 7N and 7T were divided by fractional precipitation without postchemical treatment. The efficiency of separation was estimated by the composition of poly-(oxotrimethylene) as K % in the fraction. All K % values on this paper were higher than the K % value of the template polymerization employing the homopolymer of 4-methylene-2-phenyl-2-(4-vinylphenyl)-1,3-dioxolane. It was attributed to dilution of the local concentration by the comonomer segment, which excluded the ring-intact addition to afford a grafting point between the newborn and template polymers. The prepolymer 4b containing a methyl group on the dioxolane ring gave the most excellent K % value. GPC elution curves of the newborn polymer obtained from 4b indicated that the newborn polymer was given by complete separation from the template polymer simultaneously.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Novel Template Polymerization via Radical Ring-Opening Isomerization. 2. Polymerization of Copolymer Obtained from 4-Methylene-2-phenyl-2-(4-vinylphenyl)-1,3-dioxolanes with Styrene

Sugiyama¹,

Yokozawa²,

Endo³

1994

Macromolecules

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“…Due to the variety of different processes proceeding simultaneously it makes sense to correlate the formed species with the conditions applied (Table 3) Then in 1994 a subsequent radical selective polymerization of linear polymers obtained from the conversion of 54 in DMF was tried [85]. Following an interesting mechanism a separation between a crosslinked template polymer that contains all possible structures and pure soluble poly-(oxotrimethylene) could be observed.…”

Section: -Methylene-13-dioxolanes [58]mentioning

confidence: 99%

Ring-opening polymerization of heterocycles bearing substituted and unsubstituted exo-methylene groups - a review

Klemm

Schulze

1999

Acta Polym.

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Monocyclic monomers bearing exo‐methylene groups are likely to undergo ring‐opening polymerization under the conditions of radical or cationic initiation. Several structural features will determine the course of reaction after initiation by species that exclusively attack the exo‐methylene functionality. Reviewing some of the most common classes of monocyclic heterocycles it becomes obvious that a monomer has to meet certain structural preconditions that makes them suitable for isomerizations. Among the considered heterocycles there are some types of monomers possessing an outstanding ring‐opening behavior following polymerization mechanisms free from side‐reactions. The combination of strain release due to ring‐opening isomerization, an energy decrease in the transition state caused by the formation of carbonyl‐functionalities and an appropriate stabilization of the growing chain end by steric and electronic effects may lead to clear ring‐opening mechanisms. However, this property remains restricted to only some special monomers with simple aromatic substituents being attached to the cycle. Hence a variety of cyclic ketene acetals, enolethers, (meth)acrylates, carbonates, lactones and lactames have been chosen in order to demonstrate both the possibilities and limits of ring‐opening.

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“…They undergo radical ring-opening polymerization to give polymers bearing mainly a 1, 5-ring-opened repeat unit, which introduces main-chain unsaturation [3][4][5][6][7][8][9][10] (Scheme 1). Radical polymerization in a dispersion media, particularly emulsion polymerization, is widely used to prepare paints, adhesives, coatings, fibres and construction materials.…”

Section: Introductionmentioning

confidence: 99%

Synthesis Kinetics of Polymer / Copolymer Latexes via Radical Ring-Opening Emulsion Polymerization of Vinylcyclopropane

Sarker¹,

Ebdon²,

Rimmer³

et al. 2016

J. Sci. Res.

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Radical emulsion polymerization of 1,1-bis(ethoxycarbonyl)-2-vinylcyclopropane (ECVCP) was examined in the presence of potassium persulfate (KPS) as an initiator. ECVCP underwent both emulsifier-in emulsion and emulsifier-free emulsion polymerizations to afford the ring-opened polymer in good yields. The copolymerization efficiency of this monomer was also evaluated with methyl methacrylate (MMA) and butyl methacrylate (BMA) as comonomers under the same reaction conditions. The emulsion copolymerization of ECVCP with a relatively hydrophobic monomer, lauryl methacrylate (LMA) was also investigated in presence of β-cyclodextrin hydrate (β-CD) as a phase transfer agent. Polymerization/copolymerization kinetics, change in particle size and olefin contents were followed during the reaction.

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Novel Template Polymerization via Radical Ring-Opening Isomerization. 1. Polymerization of 4-Methylene-1,3-dioxolane on the Polymer Side Chain

Cited by 6 publications

References 3 publications

Novel Template Polymerization via Radical Ring-Opening Isomerization. 2. Polymerization of Copolymer Obtained from 4-Methylene-2-phenyl-2-(4-vinylphenyl)-1,3-dioxolanes with Styrene

Novel Template Polymerization via Radical Ring-Opening Isomerization. 2. Polymerization of Copolymer Obtained from 4-Methylene-2-phenyl-2-(4-vinylphenyl)-1,3-dioxolanes with Styrene

Ring-opening polymerization of heterocycles bearing substituted and unsubstituted exo-methylene groups - a review

Synthesis Kinetics of Polymer / Copolymer Latexes via Radical Ring-Opening Emulsion Polymerization of Vinylcyclopropane

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