Synthesis and Characterization of Novel Hydrolytically Degradable Polyesters

Abstract

Six novel hydrolytically degradable polyesters were synthesized from thiodipropionic acid (TDPA) and five diols by melt polycondensation, and characterized by FT-IR, ¹H NMR, gel permeation chromatography, differential scanning calorimetry and thermogravimetry analysis. The polystyrene-equivalent number-average (M _n) and weight-average molecular weight (M _w) of these polyesters ranged from 4 900–11 100 Da and 7 900–20 879 Da, respectively, with PDI values of 1.48–1.98. The melting point varied from 62.3–127.9°C, and the 50% mass-loss temperature ranged between 387–417°C. The degradation of these polyesters was studied in terms of relative weight loss in distilled water at different pH. Weight losses of 14%–26% were obtained at pH 7.0, 26%–38% at pH 6.0, and 32%–43% at pH 8.3 over a 20-week period. The ecotoxicity study suggested that safety of the synthesized polyesters for the eisenia foetida. These results indicate that these polyesters have a combination of good thermal and degradability behaviors, which can be tailored through selection of the diol monomers used in the synthesis.

Keywords

thiodipropionic acid / water-degradable polyester / melt polycondensation / thermal properties / degradability tailoring

References

[1] Millican JM, Agarwal S. Plastic Pollution: A Material Problem[J]. Macromolecules, 2021, 54(10): 4 455-4 469.

[2] Gregory GL, Sulley GS, Peacarrodeguas L, et al. Triblock Polyester Thermoplastic Elastomers with Semi-aromatic Polymer End Blocks by Ring-opening Copolymerization[J]. Chem. Sci., 2020, 11(25): 6 567-6 581.

[3] El-Kadi SM, Elbagory M, El-Zawawy HAH, et al. Biosynthesis of Poly-Hydroxybutyrate (PHB) from Different Bacterial Strains Grown on Alternative Cheap Carbon Sources[J]. Polymers, 2021, 13(21): 3 801

[4] Pradhan S, Dikshit PK, Moholkar VS. Production, Ultrasonic extraction, and Characterization of poly (3-hydroxybutyrate) (PHB) using Bacillus Megaterium and Cupriavidus Necator[J]. Polym. Advan. Technol., 2018, 29(8): 2 392-2 400.

[5] Liu X, Li J, Huang L, et al. Preparation and Evaluation of MPEG-PCL Polymeric Nanoparticles Against Gastric Cancer[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2020, 35(6): 1 162-1 168.

[6] Damonte G, Vallin A, Fina A, et al. On the Development of an Effective Method to Produce Conductive PCL Film[J]. Nanomaterials, 2021, 11(6): 1 385

[7] Huang Y, Liu J H, Zhou T, et al. Composition Dependence of the Thermal Behavior, Morphology and Properties of Biodegradable PBS/PTMO Segment Block Copolymer[J]. J. Wuhan Univ. Technol., 2016, 31(01): 219-226.

[8] Nanni A, Messori M. Effect of the Wine Wastes on the Thermal Stability, Mechanical Properties, and Biodegradation’s Rate of Poly (3-hydroxybutyrate)[J]. Journal of Applied Polymer Science, 2021, 138(3): 49 713

[9] Almeida BC, Figueiredo P, Carvalho A. PCL Enzymatic Hydrolysis: A Mechanistic Study[J]. Acs Omega, 2019, 4(4): 6 769-6 774.

[10] Shaiju P, Bb D, Senthamaraikannan R, et al. Biodegradation of Poly (Butylene Succinate) (PBS)/Stearate Modified Magnesium-Aluminium Layered Double Hydroxide Composites under Marine Conditions Prepared via Melt Compounding[J]. Molecules, 2020, 25(23): 5 766

[11] Jacquel N, Saint-Loup R, Pascault JP, et al. Bio-based Alternatives in the Synthesis of Aliphatic-aromatic Polyesters Dedicated to Biodegradable Film Applications[J]. Polymer, 2014, 59: 234-242.

[12] Lu J, Wu L, Li B G. Long Chain Branched Poly (Butylene Succinate-co-terephthalate) Copolyesters Using Pentaerythritol as Branching Agent: Synthesis, Thermo-mechanical, and Rheological Properties[J]. J. Appl. Polym. Sci., 2016, 134(9): 44 544

[13] Qi P, Chen HL, Nguyen H, et al. Synthesis of Biorenewable and Water-degradable Polylactam Esters from Itaconic Acid[J]. Green. Chem., 2016, 18(15): 4 170-4 175.

[14] Lotti N, Finelli L, Milizia T, et al. Preparation and Thermal Behavior of Random Copolyesters of Thiodipropionic Acid[J]. Eur. Polym. J., 2000, 36(5): 929-936.

[15] Zhou XM. Synthesis and Characterization of Polyester Copolymers Based on Poly(Butylene Succinate) and Poly(Ethylene Glycol)[J]. Materials Science and Engineering: C, 2012, 32(8): 2 459-2 463.

[16] Fabbri M, Gigli M, Costa M, et al. The Effect of Plasma Surface Modification on the Biodegradation Rate and Biocompatibility of a Poly(Butylene Succinate)-based Copolymer[J]. Polym. Degrad. Stabil., 2015, 121: 271-279.

[17] Kreye O, Oelmann S, Meier MAR. Renewable Aromatic-aliphatic Co-polyesters Derived from Rapeseed[J]. Macromol. Chem. Phys., 2013, 214(13): 1 452-1 464.

[18] Valentina S, Laura G, Andrea M, et al. How Stress Treatments Influence the Performance of Biodegradable Poly(Butylene Succinate)-Based Copolymers with Thioether Linkages for Food Packaging Applications[J]. Materials, 2017, 10(9): 1 009-1 027.

[19] Taghavi N, Udugama IA, Zhuang WQ, et al. Challenges in Biodegradation of Non-degradable Thermoplastic Waste: From Environmental Impact to Operational Readiness[J]. Biotechnol. Adv., 2021, 49: 107 731.

[20] Chhazed A, Makwana MV, Chavda N, et al. Utilization of PET Waste in Plastic Bricks, Flexible Pavement & as Alternative Constructional Material-A Review[J]. International Journal of Applied Engineering Research, 2019, 14(3): 616-620.

[21] Chao GT, Fan LY, Jia W, et al. Synthesis, Characterization and Hydrolytic Degradation of Degradable Poly (Butylene Terephthalate)/Poly(Ethylene Glycol) (PBT/PEG) Copolymers[J]. J. Mater. Sci.-Mater. M, 2007, 18(3): 449