Wiktor Bukowski1, Agnieszka Bukowska1, Aleksandra Sobota2, Maciej Pytel3, Karol Bester1. 1. Faculty of Chemistry, Rzeszow University of Technology, Powstańców Warszawy 6, 35-959 Rzeszow, Poland. 2. Doctoral School of Engineering and Technical Sciences at the Rzeszow University of Technology; 35-959 Rzeszów, Poland. 3. Faculty of Mechanical Engineering and Aeronautics, Rzeszów University of Technology, Powstańców Warszawy 12, 35-959 Rzeszów, Poland.
Abstract
The effect of ligand structure on the catalytic activity of amine-bis(phenolate) chromium(III) complexes in the ring-opening copolymerization of phthalic anhydride and a series epoxides was studied. Eight complexes differing in the donor-pendant group (R1) and substituents (R2) in phenolate units were examined as catalysts of the model reaction between phthalic anhydride and cyclohexane oxide in toluene. They were used individually or as a part of the binary catalytic systems with nucleophilic co-catalysts. The co-catalyst was selected from the following organic bases: PPh3, DMAP, 1-butylimidazole, or DBU. The binary catalytic systems turned out to be more active than the complexes used individually, and DMAP proved to be the best choice as a co-catalyst. When the molar ratio of [PA]:[epoxide]:[Cr]:[DMAP] = 250:250:1:1 was applied, the most active complex (R1-X = CH2NMe2, R2 = F) allowed to copolymerize phthalic anhydride with differently substituted epoxides (cyclohexene oxide, 4-vinylcyclohexene oxide, styrene oxide, phenyl glycidyl ether, propylene oxide, butylene oxide, and epichlorohydrin) within 240 min at 110 °C. The resulting polyesters were characterized by Mn up to 20.6 kg mol-1 and narrow dispersity, and they did not contain polyether units.
The effect of ligand structure on the catalytic activity of pan class="Chemical">amine-bis(phenolate) chromium(III) complexes in the ring-opening copolymerization of phthalic anhydride and a series epoxides was studied. Eight complexes differing in the donor-pendant group (R1) and substituents (R2) in phenolate units were examined as catalysts of the model reaction between phthalic anhydride and cyclohexane oxide in toluene. They were used individually or as a part of the binary catalytic systems with nucleophilic co-catalysts. The co-catalyst was selected from the following organic bases: PPh3, DMAP, 1-butylimidazole, or DBU. The binary catalytic systems turned out to be more active than the complexes used individually, and DMAP proved to be the best choice as a co-catalyst. When the molar ratio of [PA]:[epoxide]:[Cr]:[DMAP] = 250:250:1:1 was applied, the most active complex (R1-X = CH2NMe2, R2 = F) allowed to copolymerize phthalic anhydride with differently substituted epoxides (cyclohexene oxide, 4-vinylcyclohexene oxide, styrene oxide, phenyl glycidyl ether, propylene oxide, butylene oxide, and epichlorohydrin) within 240 min at 110 °C. The resulting polyesters were characterized by Mn up to 20.6 kg mol-1 and narrow dispersity, and they did not contain polyether units.
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