Novel synthesis of polyketone via radical ring-opening polymerization of 2,2-diphenyl-4-methylene-1,3-dioxolane

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Section: Introductionmentioning

confidence: 99%

Incorporation of ketone groups into poly(4‐hydroxystyrene)s main chain by radical copolymerization of 4‐(tert‐butoxy)styrene and 2,2‐diphenyl‐4‐methylene‐1,3‐dioxolane and their photoscission

Ishikawa¹,

Morino²,

Sudo³

et al. 2010

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“…6 Some examples of the cationic ring-opening polymerization of 2-substituted-4-methylene-1,3-dioxolanes have been reported since early 1950'~,~ but those of the free radical ring-opening polymerization of them has been recently reported by us or Bailey et al For example, we have already reported that 2,2diphenyl-4-methylene-1,3-dioxolane undergoes the quantitative ring-opening reaction accompanying the elimination of benzophenone to obtain polyketone. 8 Bailey et al have also reported that 2-phenyl-4-methylene-l,3-dioxolane undergoes partial ring-opening polymeri~ation.~ In this article, we describe preparations of 2-substituted-4-methylene-1,3dioxolanes and their radical ring-opening polymerizations.…”

Section: Introductionmentioning

confidence: 84%

Preparation and radical ring‐opening polymerization of 2‐substituted‐4‐methylene‐1,3‐dioxolanes

Hiraguri¹,

Endo²

1989

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2‐Methyl‐2‐phenyl‐4‐methylene‐1,3‐dioxolane (IIa), 2‐ethyl‐2‐phenyl‐4‐methylene‐1,3‐dioxolane (IIb), 2‐phenyl‐2‐(n‐propyl)‐4‐methylene‐1,3‐dioxolane (IIc), 2‐phenyl‐2‐(i‐propyl)‐4‐methylene‐1,3‐dioxolane (IId), 2‐(n‐heptyl)‐2‐phenyl‐4‐methylene‐1,3‐dioxolane (IIe), 2‐methyl‐2‐(2‐naphthyl)‐4‐methylene‐1,3‐dioxolane (IIf), and 2,2‐diphenyl‐4‐methylene‐1,3‐dioxolane (IIg) were prepared and polymerized in the presence of a radical initiator. IIa–IIf were found to undergo vinyl polymerization with ring‐opening reaction accompanying the elimination of ketone groups in bulk. IIg was found to undergo the quantitative ring‐opening reaction accompanying the elimination of benzophenone in solution to obtain polyketone without any side reaction.

“…On the other hand, radical ring‐opening polymerization has been known as a reliable strategy for synthesis of polymers having functional groups such as ketone and ester moieties in the main chains 21, 22. Previously, we reported that 2,2‐diphenyl‐4‐methylene‐1,3‐dioxorane (DPMD) underwent the radical ring‐opening polymerization to afford the corresponding polyketone, which can be regarded as the copolymers of ethylene and carbon monoxide (Scheme ) 23–25. In addition, such radical processes offer us opportunities of radical copolymerizations of the cyclic monomers and vinyl monomers, by which the functional groups derived from the cyclic monomers can be distributed into the main chains of the polymers of the vinyl monomers.…”

Section: Introductionmentioning

confidence: 99%

Incorporation of ketone groups into poly(4‐hydroxystyrene)s main chain by radical copolymerization of 2,2‐diphenyl‐4‐methylene‐1,3‐dioxorane with O‐protected hydroxystyrenes and their photodegradable behavior

Ishikawa

Morino

Sudo

et al. 2011

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Here we report the incorporation of ketone groups into poly(4-hydroxystyrene)s main chain by radical copolymerization of O-protected hydroxystyrenes such as 4-ethoxyethoxystyrene and 4-acetoxystyrene with 2,2-diphenyl-4-methylene-1,3-dioxorane (DPMD) followed by removal of the protective groups and the photodegradable behavior of obtained copolymers. The copolymerization of O-protected hydroxystyrenes with DPMD gave the corresponding copolymers bearing DMPD-derived ketone groups in the main chain, of which content could be controlled by changing monomer feed ratio. The ethoxyethyl and acetyl groups of the obtained copolymers were completely removed under acidic and basic conditions, respectively, to afford poly(4-hydroxystyrene)s having ketone moieties in the main chain. The molecular weights of these copolymers decreased under photoirradiation due to the Norrish-type reactions of the ketone groups distributed in the main chain. These results demonstrate that poly(4-hydroxystyrene)s having ketone groups in the main chain possess good photoscissibility.