Nickel(0)-catalyzed cycloaddition copolymerization involving two diynes and carbon dioxide to poly(2-pyrone)

• Published in: Macromolecules Vol. 26; no. 18; pp. 4840 - 4844
• Main Authors: Tsuda, Tetsuo, Ooi, Osamu, Maruta, Kenichi
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.08.1993
• Subjects: 400201 - Chemical & Physicochemical Properties; ALKYNES; Applied sciences; CARBON COMPOUNDS; CARBON DIOXIDE; CARBON OXIDES; CATALYTIC EFFECTS; CHALCOGENIDES; CHEMICAL REACTION KINETICS; CHEMICAL REACTIONS; COPOLYMERIZATION; ELEMENTS; Exact sciences and technology; HETEROCYCLIC COMPOUNDS; HYDROCARBONS; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; KINETICS; METALS; NICKEL; NMR SPECTRA; ORGANIC COMPOUNDS; ORGANIC OXYGEN COMPOUNDS; Organic polymers; OXIDES; OXYGEN COMPOUNDS; Physicochemistry of polymers; POLYMERIZATION; Preparation, kinetics, thermodynamics, mechanism and catalysts; PYRANS; PYRONES; REACTION KINETICS; SPECTRA; TRANSITION ELEMENTS; Cyclopolymer; Reactivity; Steric effect; Cyclopolymerization; Carbon dioxide; Heterocyclic copolymer; Reaction mechanism; Methylene copolymer; Property structure relationship; Diynic compound; Experimental study; Complex catalyst copolymerization
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma00070a018

A copolymerizability order of five diynes, i.e., 3,11-tetradecadiyne (A), 2,6-octadiyne (B), 1,4-di(2-hexynyl)benzene (C), 1,3-di(2-hexynyl)benzene (D), and 1,7-cyclotridecadiyne (E), in the nickel(0)-catalyzed 1:1 cycloaddition copolymerization of the diyne with CO[sub 2] to the poly(2-pyrone) was determined by the nickel(0)-catalyzed copolymerization involving two diynes and CO[sub 2]. The copolymerizability order obtained by analyzing the copolymer composition using [sup 1]H NMR spectroscopy was A [gt] E [gt] B [gt] C [gt] D. This order was explained in terms of the steric hindrance exerted by the substituent on the terminal C[triple bond]C bond of the cooligomer or the copolymer to its cycloaddition along with mobility of its terminal C[triple bond]C bond moiety for the cycloaddition. An order of cycloaddition reactivity of the diyne, which is related to formation of the cooligomer, was determined by measuring the unreacted diyne in the copolymerization involving five diynes and CO[sub 2] using gas chromatography. The result was E [gt] B [gt] C [gt] D [gt] A. Thus high copolymerizability of diyne A is noteworthy.