High Molecular Weight Poly(1-Oxo-Trimethylene) Solution Obtained by the Catalytic

High molecular weight poly(1-oxo-trimethylene) solution obtained by the catalytic copolymerization of CO with ethene in phenol-H2O as a solvent

Andrea Vavasoria and Lucio Ronchina

aDepartment of Scienze Molecolari e Nanosistemi, University Ca’ Foscari Venice, Dorsoduro 2137, 30123 Venice, Italy

The CO-ethene copolymerization, catalyzed by Pd(II)-diphosphine complexes, affords to the perfectly alternate poly(1-oxo-trimethylene), a high-performance thermoplastic with interesting physical and chemical properties [1]. The catalysis is efficiently carried out in methanol where the Pd(II) precursors are soluble while the polymer is insoluble [1]. As a consequence of this, during the reaction the Pd(II) intermediates, bonded with the growing polymer chain, precipitate after insertion of only a few monomers units and the polymer growth continues through a liquid-solid heterogeneous catalysis. We propose the homogeneous CO-ethene copolymerization carried out in phenol-H2O as a solvent and the influence of such a solvent on the molecular weight and on the productivity have been investigated.

The [Pd(OAc)2dppp] complex (dppp 1,3 bis(diphenylphosphino)propane), used as catalyst precursor, is inactive both in pure phenol and in pure H2O, but it turns active in a proper phenol-H2O mixture. The productivity passes through a maximum of 6050 g polymer/(gPd.h) at H2O ca. 30 molar %, and a homogeneous colorless polymer solution is obtained. The molecular weight of the poly(1-oxo-trimethylene) increases by increasing the H2O concentration. Catalysis is favored by acids [1,2] and, in such a solvent, among the acids tested [1,2], formic acid affords to the best productivity, 10500 g/(gPd.h).

References
[1] Drent E., Budzelaar P. H. M., Chem. Rev. 1996, 96, 663.

[2] Vavasori A., et al. , J. Mol. Catal. A: Chemical 2003, 204, 295.

Document ID: IUPAC1601

Title: High molecular weight poly(1-oxo-trimethylene) solution obtained by the catalytic copolymerization of CO with ethene in phenol-H2O as a solvent

Meeting: 43nd IUPAC World Chemistry Congress, 30-July through 7-August, 2011 in San Juan, Puerto Rico