Synthesis and characterization of α-(cyclic carbonate), ω-hydroxyl/itaconic acid asymmetric telechelic poly(ε-caprolactone)

• Published in: Polymer bulletin (Berlin, Germany) Vol. 72; no. 10; pp. 2489 - 2501
• Main Authors: Patil, Ravindra Mahadev, Hong, Han, Chai, Christina L. L., Ghanwat, Anil A., Ganugapati, Satyanarayana, Gnaneshwar, Rudhramyna
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.10.2015; Springer Nature B.V
• Subjects: Asymmetry; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Chromatography; Cold; Complex Fluids and Microfluidics; Glycerol; High temperature; Initiators; Isocyanates; Itaconic acid; Molecular weight; NMR; Nuclear magnetic resonance; Organic Chemistry; Original Paper; Phenylethylamine; Physical Chemistry; Polycaprolactone; Polyesters; Polymer Sciences; Polymerization; Polymers; Ring opening polymerization; Soft and Granular Matter; Ring-opening polymerization; Functional initiators; Reactive and functional polymers; Biodegradable polymers; Telechelics
• ISSN: 0170-0839; 1436-2449
• DOI: 10.1007/s00289-015-1413-5

Well-defined α-(cyclic carbonate), ω-hydroxyl asymmetric telechelic poly(ε-caprolactone)s (PCLs) were prepared with good end-group fidelity by ring-opening polymerization (ROP) of ε-CL catalyzed by Sn(Oct) 2 in conjunction with a renewable, functional bio-based initiator namely glycerol 1,2-carbonate (GC) in bulk at 110 °C. The end group’s structure derived from the alcohol initiator was confirmed by NMR, FTIR and MALDI TOF MS. The living character of ROP of ε-CL using GC/Sn(Oct) 2 was demonstrated by the linear correlation of molecular weight versus monomer conversion. End-capping reaction of α-(cyclic carbonate), ω-hydroxyl asymmetric telechelic PCL with itaconic anhydride to yield α-(cyclic carbonate), ω-(itaconic acid) asymmetric telechelic PCL was presented. Five-membered cyclic carbonate end group reaction with 2-phenylethylamine enabled the hydroxyurethane end functional PCL without the use of the relatively more hazardous isocyanates and without any by-product.