Ketene acetal monomers: Cationic photopolymerization

Crivello, James V.; Lai, Yi‐Chun; Malik, Ranjit

doi:10.1002/(sici)1099-0518(19961115)34:15<3103::aid-pola2>3.0.co;2-y

Cited by 13 publications

(11 citation statements)

References 25 publications

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“…183 This trend was observed with other CKA monomers. 181 It has also been shown that addition of a solvent also facilitated the ring-opening, which was explained by favored intramolecular mechanisms (CKA ring-opening in this case), upon dilution. 27 For example, in the presence of tert-butyl peroxide at 110 °C, the two monosubstituted 5-membered CKA (CKA3 and CKA4, Figure 72) led to polyester at 73 and 90 % when polymerized in bulk, whereas 100% of ring-opening were observed when the polymerization was performed in 50 wt% benzene.…”

Section: Influence Of the Experimental Conditionsmentioning

confidence: 76%

“…The cationic ring-opening polymerization of monomers with methyl or ethyl group on the C=C double bond gave interesting results by varying the ratio of vinyl versus ring opening process. Crivello and co-workers 181 reported that an efficient control of the polymerization rate was possible with a photochemical initiating system based on diaryliodonium and triarylsulfonium salts at room temperature (Figure 71). The reactivity of CKA monomers displayed on Figure 71 strongly depends on the monomer structure.…”

Section: Cationic Polymerizationmentioning

confidence: 99%

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Radical Ring-Opening Polymerization: Scope, Limitations, and Application to (Bio)Degradable Materials

et al. 2017

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Cyclic monomers bearing either vinyl or exomethylene groups have the ability to be polymerized through a radical pathway via a ring-opening mechanism (addition-fragmentation process), leading to the introduction of functionalities in the polymer backbone. Radical ring-opening polymerization (rROP) combines the advantages of both ring-opening polymerization and radical polymerization, that is the preparation of polymers bearing heteroatoms in the backbone but with the ease and robustness of a radical process. This current review presents a comprehensive description of rROP by detailing: (i) the various monomers that polymerize through rROP; (ii) the main parameters that govern the rROP mechanism; (iii) the copolymerization by conventional or controlled/living radical polymerization between rROP monomers and traditional vinyl monomers to obtain copolymers with advanced properties; (iv) the different applications (low shrinkage materials and preparation of (bio)degradable materials) of rROP monomer-containing materials, and (v) the main alternatives to rROP to induce degradability to materials obtained by a radical polymerization.

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Section: Influence Of the Experimental Conditionsmentioning

confidence: 76%

Section: Cationic Polymerizationmentioning

confidence: 99%

Radical Ring-Opening Polymerization: Scope, Limitations, and Application to (Bio)Degradable Materials

et al. 2017

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“…If one compares the results for less substituted 2-methylene-1.3-dioxepanes with each other, the statement that such compounds exclusively undergo complete ring-opening should be treated critically. In some previous studies whether the parent compound 92 [125] nor 2-ethylidene-1.3-dioxepane 96 [52] were found to fulfill this assumption completely. Moreover, the cationic polymerization of 2ethylidene-1.3-dioxepane 96 ends up with about 60% ringopening which is in agreement with the excepted steric hindrance for electrophilic attack.…”

Section: -Methylene-13-dioxepanesmentioning

confidence: 98%

“…Recently Crivello and coworkers have found access to a series of five-and six-membered ketene acetals (33 a -e, 34 a -f) with alkyl-groups attached to the exo-methylene group [51,52]. As it is further known, ketene acetals having outer substitution shouldn't be able to undergo radical induced polymerizations or the radical attack should at least be retarded.…”

Section: -Methylene-13-dioxolanesmentioning

confidence: 99%

“…Crivello et al have reported the photopolymerization of 2-ethylidene-1.3-dioxane 82 and 2-ethylidene-4-methyl-1.3-dioxane 83, respectively [51,52]. Beside the general considerations given there concerning the role of outer substituents on the polymerization ability both monomers were found to undergo 45% (for 82) and 81% ring-opening (for 83).…”

Section: 3-dioxanesmentioning

confidence: 99%

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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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Cationic polymerization of cyclic ketene acetals via zwitterion formation with cyanoallene

Yamamoto

Sanda

Endō

2000

J. Polym. Sci. A Polym. Chem.

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This article deals with the polymerization of the cyclic ketene acetals (CKAs) 2‐methylene‐4‐phenyl‐1,3‐dioxolane (2), 2‐methylene‐4‐phenyl‐1,3‐dioxane (3), 4,7‐dimethyl‐2‐methylene‐1,3‐dioxepane (4), 2‐ethylidene‐4‐phenyl‐1,3‐dioxolane (5), 2‐phenylmethylene‐1,3‐dioxolane (6), and 2‐isopropylidene‐4‐phenyl‐1,3‐dioxolane (7) in the presence of cyanoallene (1). For 2 and 3, the homopolymerization of the CKAs proceeded without ring opening, and the number‐average molecular weights of the obtained polymers depended on the feed ratio of 1. However, the reactions of 1 with 4–7 afforded no polymers but did afford spirocyclic 1 : 1 adducts possessing cyclobutane rings. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2075–2081, 2000

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Ketene acetal monomers: Cationic photopolymerization

Cited by 13 publications

References 25 publications

Radical Ring-Opening Polymerization: Scope, Limitations, and Application to (Bio)Degradable Materials

Radical Ring-Opening Polymerization: Scope, Limitations, and Application to (Bio)Degradable Materials

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

Cationic polymerization of cyclic ketene acetals via zwitterion formation with cyanoallene

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