Synthesis and Structure-Property Relationship of Amphiphilic Poly(2-ethyl- co-2-(alkyl/aryl)-2-oxazoline) Copolymers

Taha Behroozi Kohlan; Asu Ece Atespare; Mehmet Yildiz; Yusuf Ziya Menceloglu; Serkan Unal; Bekir Dizman

doi:10.1021/acsomega.2c04809

Synthesis and Structure-Property Relationship of Amphiphilic Poly(2-ethyl- co-2-(alkyl/aryl)-2-oxazoline) Copolymers

ACS Omega. 2022 Oct 26;7(44):40067-40077. doi: 10.1021/acsomega.2c04809. eCollection 2022 Nov 8.

Authors

Taha Behroozi Kohlan^{1

2}, Asu Ece Atespare^{1

2}, Mehmet Yildiz^{1

2}, Yusuf Ziya Menceloglu^{1

2}, Serkan Unal^{1

2}, Bekir Dizman^{1

2}

Affiliations

¹ Integrated Manufacturing Technologies Research and Application Center & Composite Technologies Center of Excellence, Sabanci University, Istanbul 34956, Turkey.
² Faculty of Engineering and Natural Sciences, Materials Science and Nano Engineering, Sabanci University, Istanbul 34956, Turkey.

Abstract

Poly(2-oxazoline)s (POZs) are widely investigated for their applications in various fields due to their unique properties. To exploit and combine different characteristics of the POZ family, 2-oxazoline monomers can be copolymerized to prepare tailor-made copolymers with the desired glass transition temperature (T _g), melting temperature (T _m), amphiphilicity, and functionality. Here, we report the synthesis and characterization of 2-oxazoline monomers and a range of POZ copolymers produced, thereof. 2-Propyl-2-oxazoline (PrOZ) and 2-pentyl-2-oxazoline (PeOZ) monomers were synthesized by two different methods starting from nitriles or carboxylic acids. A number of POZ copolymers were synthesized by copolymerization of 2-ethyl-2-oxazoline (EOZ) with either one of PrOZ, PeOZ, or 2-phenyl-2-oxazoline (PhOZ) at three different compositions (25:75, 50:50, and 75:25) and three molecular weights (1000, 2000, and 5000 Da). The successful synthesis of the monomers and copolymers was demonstrated through their structural analysis by ¹H NMR and FTIR. SEC results confirmed the targeted molar masses of the copolymers and living nature of the polymerization by showing low dispersity values. Thermal properties of the copolymers were studied using DSC and TGA. DSC studies revealed the amorph and random state of the copolymers with obtained T _g values for the copolymers in the range of -3 to 84 °C depending on their molecular weight and type of the side chain. While the presence of longer aliphatic side chains resulted in lower T _g values, the presence of 2-phenyl substituents on the polymer led to higher T _g values. The decomposition temperatures determined by TGA were in the range of 328 to 383 °C depending on the molecular weight, composition, and side chain of the copolymers. It was observed that higher molecular weights led to higher T _g values and decomposition temperatures. While copolymers with aliphatic side chains exhibited a single-step decomposition profile, the decomposition of copolymers having aromatic side chains occurred in multiple steps. The variations in the molecular weight, composition, and side chains of the copolymers resulted in a library of tailorable amphiphilic copolymers suitable for multiple applications ranging from biomedical applications to composite manufacturing.