Enzymatic Catalysis in Favor of Blocky Structure and Higher Crystallinity of Poly(Butylene Succinate)-Co-(Dilinoleic Succinate) (PBS-DLS) Copolymers of Variable Segmental Composition

Martyna Sokołowska; Jagoda Nowak-Grzebyta; Ewa Stachowska; Miroslawa El Fray

doi:10.3390/ma15031132

Enzymatic Catalysis in Favor of Blocky Structure and Higher Crystallinity of Poly(Butylene Succinate)-Co-(Dilinoleic Succinate) (PBS-DLS) Copolymers of Variable Segmental Composition

Materials (Basel). 2022 Feb 1;15(3):1132. doi: 10.3390/ma15031132.

Authors

Martyna Sokołowska¹, Jagoda Nowak-Grzebyta^{2

3}, Ewa Stachowska³, Miroslawa El Fray¹

Affiliations

¹ Department of Polymer and Biomaterials Science, Faculty of Chemical Technology and Engineering, West Pomeranian University of Technology, Al. Piastow 45, 71-311 Szczecin, Poland.
² Institute of Materials Technology, Poznan University of Technology, ul. Piotrowo 3, 60-965 Poznan, Poland.
³ Division of Metrology and Measurement Systems, Institute of Mechanical Technology, Poznan University of Technology, ul. Piotrowo 3, 60-965 Poznan, Poland.

Abstract

To systematically investigate the synthesis of poly(butylene succinate)-co-(dilinoleic succinate) (PBS-DLS) copolymers and to enrich the library of polyesters synthesized via a sustainable route, we conducted a two-step polycondensation using fully biobased monomers such as diethyl succinate (DS), 1,4-butanediol (1,4-BD) and dilinoleic diol (DLD) in diphenyl ether, using Candida Antarctica lipase B (CAL-B) as biocatalyst. A series of PBS-DLS copolyesters with a 90-10, 70-30 and 50-50 wt% of hard (PBS) to soft (DLS) segments ratio were compared to their counterparts, which were synthesized using heterogenous titanium dioxide/silicon dioxide (TiO₂/SiO₂) catalyst. Chemical structure and molecular characteristics of resulting copolymers were assessed using nuclear magnetic spectroscopy (¹H- and ¹³C-NMR) and gel permeation chromatography (GPC), whereas thermal and thermomechanical properties as well as crystallization behavior were investigated by differential scanning microscopy (DSC), dynamic mechanical thermal analysis (DMTA), digital holographic microscopy (DHM) and X-ray diffraction (XRD). The obtained results showed that, depending on the type of catalyst, we can control parameters related to blockiness and crystallinity of copolymers. Materials synthesized using CAL-B catalysts possess more blocky segmental distribution and higher crystallinity in contrast to materials synthesized using heterogenous catalysts, as revealed by DSC, XRD and DHM measurements.

Keywords: CALB; PBS copolymer; block copolymers; enzymatic synthesis; poly(butylene succinate).

Abstract

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