4-phenyl-1,3-dioxolane, polymerization

Jonsson et al., studied a difunctional maleimide with two different electron donors, a vinyl ether and phenyl dioxolane. They observed that structural modifications increase the electron density in the vinylic C=C bond of the donor monomer and promote higher rates of co-polymerization with maleimides. They also compared a vinyl ether with exomethylenic dioxolane and showed increased "reactivity" for the dioxolane monomer. As a result, the mechanism of reaction of maleimide with a donor monomer, a vinyl ether was... 

TABLE 1. Copoly merization Scoping Reactions Using the Radical Ring-Opening Polymerization Monomer, 5-Methylene-2-phenyl-l,3-dioxolan-4-one, with Methyl Methacrylate... 

The preparation of the radical ring-opening polymerization monomer, 5-methylene-2-phenyl-l,3-dioxolan-4-one, (I), is illustrated in Eq. (1). 

The extruder can be used for a variety of polymerizations even if no preformed polymer is present.89 These include the continuous anionic polymerization of caprolactam to produce nylon 6,90 anionic polymerization of capro-lactone 91 anionic polymerization of styrene 92 cationic copolymerization of 1,3-dioxolane and methylal 93 free radical polymerization of methyl methacrylate 94 addition of ammonia to maleic anhydride to form poly(succin-imide) 95 and preparation of an acrylated polyurethane from polycaprolactone, 4,4 -methylenebis(phenyl isocyanate), and 2-hydroxyethyl acrylate.96 The technique of reaction injection molding to prepare molded parts is slightly different. Polyurethanes can be made this way by... 

Some cyclic acetals may have a low ceiling temperature and polymerization may ensue at a lower temperature than applied. We recall here the polymerization of 4-phenyl-1,3-dioxolane (considered earlier nonpolymerizable) at —20 °C by Elias et al. 6). The Tc of 4-phenyl-1,3-dioxolane is 20 °C 6). 

Grafting with a well defined number of active sites has also been performed. It was established earlier that 2-phenyl-1,3-dioxolan-2-ylium salts initiate the polymerization of THF by direct addition and proceed with opening of the C-4/0-3 bond in the dioxolenium cation 151). Thus, Okada et al. have prepared dioxolenium salts coupled to phenyl rings in polystyrene 152) ... 

Also, cross-linked polyesters can be easily made by reaction of CKAs with vinyl cross-linkers with more than one double bond. In one of the studies, porous monolithic supports for tissue engineering were made by electron-beam-initiated free-radical polymerization of 2-methylene-4-phenyl-l,3-dioxolane with trimethylolpropane triacrylate as a cross linker [24]. 

Pan, C.Y. and Lou, X.D. (2000) Living free radical ring-opening polymerization of 2-methylene-4-phenyl-l,3-dioxolane by atom transfer radical polymerization. Macromol. Chem. Phys., 201, 1115. 

The palladium(ii) acetylacetonate-tri phenyl phosphine catalysed reaction of butadiene with water and carbon dioxide in solvents such as t-butanol or acetone has been reported to give octa-2,7-dien-l-ol as the major product together with minor amounts of octa-l,7-dien-3-ol, 1,3,7-octatriene and octadienyl ethers. In contrast aqueous potassium tetrachloropalladate with excess diene leads to pale yellow solids which were polymeric. Decomposition of these complexes with dimethylglyoxime gave a mixture of 3-methyIbutenyl ethers, (Scheme 33). The use of (—)-2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-l,3-dioxolane (DIOP) as a chiral ligand... 

Vinyl-functional alkylene carbonates can also be prepared from the corresponding epoxides in a manner similar to the commercial manufacture of ethylene and PCs via CO2 insertion. The most notable examples of this technology are the syntheses of 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate, VEC) (5, Scheme 24) from 3,4-epoxy-1-butene or 4-phenyl-5-vinyl-l,3-dioxolan-2-one (6, Scheme 24) from analogous aromatic derivative l-phenyl-2-vinyl oxirane. Although the homopolymerization of both vinyl monomers produced polymers in relatively low yield, copolymerizations effectively provided cyclic carbonate-containing copolymers. It was found that VEC can be copolymerized with readily available vinyl monomers, such as styrene, alkyl acrylates and methacrylates, and vinyl esters.With the exception of styrene, the authors found that VEC will undergo free-radical solution or emulsion copolymerization to produce polymeric species with a pendant five-membered alkylene carbonate functionality that can be further cross-linked by reaction with amines. Polymerizations of 4-phenyl-5-vinyl-l,3-dioxolan-2-one also provided cyclic carbonate-containing copolymers. 

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