Polymerization via zwitterion 27. No-catalyst copolymerization of 2-phenyl-1,3,2-dioxaphospholane with β-hydroxyalkyl acrylates and methacrylates
TL;DR: In this paper, the authors describe no-catalyst copolymerizations between polyphosphinate type copolymers and four β-hydroxyalkyl acrylates.
Abstract: This paper describes “No-Catalyst Copolymerizations” between ethylene phenylphosphonite (EPO) as MN and four β-hydroxyalkyl acrylates and methacrylates as ME. In all combinations polyphosphinate type copolymers were obtained above 130 °C without added catalyst. The first step of reaction was a proton-transfer step to yield a transient phosphonium-alkoxide zwitterion 5 and generated a phosphorane intermediate like 6. The subsequent reactions of 6 were rather complicated. It was possible to conceive several zwitterions to lead to polymer units. The liberation of ethylene oxide and/or propylene oxide was observed as a side reaction during polymerization.
Citations
More filters
01 Jan 1985
TL;DR: In this paper, the authors describe alternating copolymerization in which two kinds of monomer interact with each other to generate zwitterion intermediates leading to the production of alternatingcopolymers.
Abstract: This chapter describes alternating copolymerizations in which two kinds of monomer interact with each other to generate zwitterion intermediates leading to the production of alternating copolymers. Since zwitterions are responsible for both initiation and propagation in these systems, it is not necessary to employ a catalyst (initiator) or high-energy irradiation to induce the copolymerization. Thus, this type of copolymerization is sometimes called “no-catalyst alternating copolymerization via zwitterion intermediates” or “spontaneous alternating copolymerization via zwitterion intermediates.” These alternating copolymerizations have been developed mainly by the present authors and co-workers in the past decade.(1)
14 citations
01 Jan 2012
TL;DR: In this paper, the ring-opening polymerization of cyclic organophosphorus compounds is discussed and the synthesis of polyphosphazenes and related polymers is discussed.
Abstract: This chapter describes the ring-opening polymerization of cyclic phosphorus-containing (P-containing) monomers and consists of two parts. In the first part, the ring-opening polymerization of cyclic organophosphorus compounds is discussed. The second part is devoted to the synthesis of polymers having inorganic backbones, mainly polyphosphazenes and related polymers. The synthesis of P-containing polymers by polyaddition is only mentioned for the reaction of phosphoric acid derivatives with diepoxides. Kinetics and mechanism of polymerization are described for the selected monomers. Some properties and applications of the resulting polymers are also reported.
8 citations
TL;DR: In this paper, Copolymeres alternes a partir de dioxaphospholannes, imine ethers, and lactones with lacide acrylique.
6 citations
References
More filters
20 citations
TL;DR: In this paper, the first isolated instance of spiro acyloxyphosphoranes was described emphasizing the significance of the isolated instances of these new species, and the no-catalyst alternating copolymerization of the combinations of cyclic phosphorus(III) compounds with acrylic acid derivatives and with α-keto acids (electrophilic monomer, ME) are mentioned.
Abstract: Novel methods of synthesis of spiro acyloxyphosphoranes are described emphasizing the significance of the first isolated instance of these new species. Then, the no-catalyst alternating copolymerizations of the combinations of cyclic phosphorus(III) compounds (serving as nucleophilic monomer, MN) with acrylic acid derivatives and with α-keto acids (electrophilic monomer, ME) are mentioned. These copolymerizations proceed without added initiator. Spiro oxyphosphoranes play an important role in the copolymerization scheme in the equilibrium with the +MN - ME − zwitterion, the key intermediate of the copolymerization. Finally, new reactions of spiro acyloxyphosphoranes with nucleophiles, alcoholysis and aminolysis polymerizations are presented.
10 citations