A Novel Living Coordination Polymerization of Methoxyallene by .pi.-Allylnickel Catalyst

Abstract

A coordination polymerization of alkoxyallenes (2a-2f) by the [q3-(allyl)NiOCOCF3] (1) /PPh, system was carried out to obtain a polymer (3) bearing exomethylenes on the main chain. The structure of the obtained polymer was confirmed by 'H-, "C-NMR and IR spectra, and was revealed to consist of two units, one bearing an exomethylene side chain and the other an end ether side chain as a result of 1,2-and 2,3-~olymerization. In the case of methoxyallene, the ratio was estimated as 32:68. The number average molecular weight (M&f t& resulting polymer varied linearly with increasing ratio of monomer to initiator. The molecular weight distributions (MJM,,) of the polymers obtained here were always approximately 1.1.These results may strongly support that the present polymerization proceeds bya living mechanism. Under an inert atmosphere, the propagating end of the polymer was quite stable and could be kept without any decrease in activity for more than a week. The proportion of 1,2-and 2,3-polymerization was a little affected by the substituents on the alkoxyallenes, as the steric bulkiness of the substituents increased the content of 2,3-polymerization units.

Well-defined polymer microspheres formed by living dispersion polymerization: precisely functionalized crosslinked polymer microspheres from monomers possessing cumulated double bonds

“…33 Monomers (2a-g) were prepared as reported previously. 33,34,48 Polyvinylpyrrolidone (PVP) (M w = 10 000 and 360 000) and poly(ethylene glycol) (M w = 8500) were obtained from Tokyo Chemical Industry and were used as received. Propyl cellulose and 2-hydroxypropyl cellulose were obtained from Wako Pure Chemical Industry and were used as received.…”

“…A toluene solution of [(π-allyl)-NiOCOCF 3 ] 2 /PPh 3 (1) was prepared as described previously. 33 Monomers (2a-g) were prepared as reported previously. 33,34,48 Polyvinylpyrrolidone (PVP) (M w = 10 000 and 360 000) and poly(ethylene glycol) (M w = 8500) were obtained from Tokyo Chemical Industry and were used as received.…”

“…In fact, this living polymerization can be applied to monomers bearing diverse functional groups such as alkyl, aryl, alkoxy, carboalkoxy, hydroxy and amide to produce welldefined polymers bearing the corresponding functional groups. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] Additionally, this living polymerization can be carried out in protic polar media such as alcohols without any deactivations of the growing species. 47 In this paper, we describe the results of the π-allylnickelcatalyzed living dispersion polymerization of allene derivatives that enables the precision synthesis of well-defined polymer microspheres.…”

Polymerization of n‐Octylallene with Rare Earth Catalyst Composed of Ln(P204)3/Al(i‐Bu)3

“…3 Endo and co-workers developed the living coordination polymerization of allene derivatives by π-allylnickel catalysts. [4][5][6][7] Recently, we reported the polymerization of n-octylallene with the coordination catalyst system composed of bis[N,N-(3,5-di-tertbutylsalicylidene)anilinato] titanium(IV) dichloride (Ti(Salen) 2 Cl 2 ) and Al(i-Bu) 3 . 8 Further, possibilities for the designed synthesis of allene monomers with a wide variety of substituents having various functional groups may indicate the potential applicability of polymers from allene derivatives as novel reactive polymers as well as novel functional materials.…”

Radical Copolymerization of 2,4-Disubstituted Enynes with Electron-Accepting Comonomers

“…For example, the living coordination polymerization of a variety of allenes was achieved by π-allylnickel catalysts. [1][2][3][4][5] The resulting polymers contained either one part of double-bond moieties quantitatively.…”