Abstract
A new series of potentially biobased copolyesters, poly(1,3-butylene 1,4-cyclohexylenedimethylene terephthalate) (P13BCT) based on 1,3-butanediol (1,3-BD) with 1,4-cyclohexane dimethanol (CHDM) was synthesized. Dibutyltin oxide (DBTO) and titanium(IV) butoxide (TBT) catalysts were employed, and the resulting copolymers were analyzed to evaluate the efficacy of each catalyst on the copolymerization. DBTO produced low molecular weight oligomers with Mn ranging from 2,000 to 2,500, whereas TBT produced high molecular weight copolymer Mn ranging from 8,700∼21,900. GC-MS analysis was performed to identify the by-products during the transesterification process, and side reactions such as dehydration were observed, which were in good agreement with previous results showing the same by-product. The correlation spectroscopy (COSY), heteronuclear single-quantum correlation spectroscopy (HSQC), 1H and 13C NMR analyses revealed that the chain end of P13BCT_Sn was primarily composed of the vinyl end group rather than the hydroxyl group, which was a major contributor to the formation of low molecular weight polymers. The density of P13BCT slightly increased with the addition of 1,3-BD. The Tg of P13BCT decreased with 1,3-BD contents from 74 °C to 51 °C due to the enhanced flexibility of the main chain. The thermal stability of the copolyesters was determined using TGA in a nitrogen atmosphere. The copolyesters were stable up to 330–360 °C, and the decomposition temperature decreased as the 1,3-BD content increased. Yield strength increased from 39.4 MPa to 43.6 MPa as 1,3-BD content increased; however, Young’s modulus and yield strength difference was not statistically significant.
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Acknowledgment: This work was supported by the Chemical R&D Institute, SK Chemicals and the National Research Foundation of Korea (NRF) grant funded by the Korea government (Ministry of Science, ICT; MSIT) (NRF-2019R1A2C2008249). The Institue of Engineering Research at Seoul National University provided research facilities for this work.
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Kim, JH., Kim, M.S., Kim, H.J. et al. Novel Potentially Biobased Copolyesters Comprising 1,3-Butanediol, 1,4-Cyclohexanedimethanol and Dimethyl Terephthalate; Effect of Different Catalysts on Polymerization Behavior. Macromol. Res. 30, 51–60 (2022). https://doi.org/10.1007/s13233-022-0008-x
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DOI: https://doi.org/10.1007/s13233-022-0008-x