Propene−Norbornene Copolymers. Toward a Description of Microstructure at Triad Level Based on Assignments of 13C NMR Spectra

• Published in: Macromolecules Vol. 43; no. 10; pp. 4543 - 4556
• Main Authors: Boggioni, Laura, Ravasio, Andrea, Boccia, Antonella Caterina, Ferro, Dino Romano, Tritto, Incoronata
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 25.05.2010
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Properties and characterization; Structure, morphology and analysis; Norbornene copolymer; Propylene copolymer; Molecular structure; Heteronuclear decoupling; NMR spectrometry; Experimental study; Two dimension spectrometry; Random copolymer; Investigation method; Spectrum analysis; Proton; Triad; Microstructure; Carbon 13
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma100268h

A procedure for the quantitative determination of the molar fractions of the stereosequences defining the microstructure of a propene−norbornene (P−N) copolymer from 13C NMR spectra has been set up. This method utilizes the observed peak areas of the 13C signals and takes into account the consistency between peak areas and the stoichiometry of the copolymer chain. With the support of homonuclear 1H−1H and heteronuclear 1H−13C NMR techniques, by guessing assignments of unknown signals, and by discarding inconsistent hypotheses, an extension of signal assignments is made possible. This procedure, which allows for a quantitative analysis of copolymer sequences as accurate as possible, has been applied to the analysis of the 13C NMR spectra of a number of P−N copolymers prepared with catalyst precursors rac-Et(Indenyl)2ZrCl2 (1) and rac-Me2Si(2-Me-Indenyl)2ZrCl2 (2). A complete description of the microstructure at triad level, including 1,3- and 2,1-propene insertions, has been attempted. New signals have been assigned such as those of the carbons of propene in the alternating triad NP 12 N and of norbornene in tetrad NP 12 N P 12, as well as the signals of P β methyl groups in triad NP 12 P 12 adjacent to a variable number of P 12 units all in isotactic relationship and those of the S αγ methylene of a 1,3 propene inserted unit in the NP 13 P 12 and of the methyl carbon atom of central monomer in P 21 P 12 N and NP 21 P 12. Although the goal of determining all the triads has not been achieved, an estimate of the molar fractions of the major sequences with a standard deviation on the order of 2−4% has been obtained. The quantitative determination of copolymer microstructure will allow one to clarify the P−N copolymerization mechanism.