Synthesis and Characterization of Poly(linoleic acid)-g-Poly(εcaprolactone) ve Poly(linolenic acid)-g-Poly(ε-caprolactone) Graft Copolymers via Ring Opening Polymerization

Year 2018, Volume: 6 Issue: 4, 1010 - 1027, 01.08.2018

Sema Allı Pinar Geçit Murat Gürel Abdulkadir Allı

https://doi.org/10.29130/dubited.433999

Cited By: 1

Abstract

In this study, PLina /PLinl peroxides were obtained by the auto-oxidation of linoleic acid (Lina) and linolenic acid (Linl) respectively. The autooxidation of Lina and Linl under air condition at room temperature rendered waxy soluble polymeric peroxide, having soluble fraction more than 98 weight percent (wt%) and containing up to 1.10-1.20 wt % of peroxide. Biodegradable poly (linoleic acid)-g-poly(ε-caprolactone) and poly (linolenic acid)-g-poly(ε-caprolactone) graft copolymers were synthesized via ring opening polymerization between autoxidized linoleic acid and linolenic acid peroxide initiators's carboxylic acid groups and ε-caprolactone monomer. The intrinsic viscosity values of poly (linoleic acid)-g-poly(ε-caprolactone) and poly (linolenic acid)- g-poly(ε-caprolactone) graft copolymers were determined. The graft copolymers obtained were characterized by 1H NMR, FT-IR, TGA, DSC and GPC techniques

Keywords

Autooxidation, caprolacton, Linoleic acid, Intrinsic Viscosity

Halka Açılma Polimerizasyonuyla Poli(linoleik asit)-g-Poli(ε-kaprolakton) ve Poli(linolenik asit)-g-Poli(ε-kaprolakton) Graft Kopolimerlerin Sentezi ve Karakterizasyonu

Abstract

Bu
çalışmada, linoleik asit (Lina) ve linolenik asit (Linl)’ler otooksidasyona
uğratılarak polimerik linoleik asit
peroksit (PLina) ve polimerik linolenik asit peroksit (PLinl) elde edildi. Lina
ve Linl’lerin otooksidasyonu hava ortamında oda sıcaklığında gerçekleştirilerek
% 1.10-1.20 peroksit içeren, % 98 çözünür kısımlarına sahip yapıları elde
edildi. Biyobozunur poli(linoleik asit)-g-poli(ε-kaprolakton)
ve poli(linolenik asit)-g-poli(ε-kaprolakton)
graft kopolimerler, otookside olmuş linoleik asit ve linolenik asit’lerin
karboksilik asit grupları ile 
ε-kaprolakton monomeri arasındaki halka açılma polimerizasyonuyla elde
edildiler. Poli(linoleik
asit)-g-poli(ε-kaprolakton) ve poli(linolenik asit)-g-poli(ε-kaprolakton) graft
kopolimerlerin instristik viskozite değerleri belirlendi. Elde edilen graft
kopolimerlerin karakterizasyonları ¹H NMR, FT-IR,
 TGA, DSC ve GPC teknikleri kullanılarak
yapıldı. 

Keywords

Otooksidasyon, ε-kaprolakton, Linoleik asit, Linolenik asit, İnstristik Viskozite

References

• J. J. Bozell, “Feedstocks for the Future Biorefinery Production of Chemicals from Renewable Carbon”, Clean Soil, Air, Water, 36 (8), 641-647, 2008.
• C. K. Williams and M. A. Hillmyer, “Polymers from renewable resources: a perspective for a special issue of polymer reviews”, Polym. Rev. 48 (1), 1–10, 2008. 1–10.
• M. Eissen, J. O. Metzger, E. Schmidt, U. Schneidewind, “10 Years after Rio-Concepts on the Contribution of Chemistry to a Sustainable Development”, Angew. Chem. Int. Ed., 41, 414 – 436, 2002.
• G.W. Huber, S. Iborra and A. Corma, “Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering”, Chem. Rev., 106, 4044–4098, 2006.
• M. N. Belgacem and A. Gandini, in Monomers, Polymers and Composites from Renewable Resources, ed. M. N. Belgacem and A. Gandini, Elsevier, Amsterdam, pp. 39–66, 2008.
• A. Demirbas, “New Biorenewable Fuels from Vegetable Oils”, Energy Sources, Part A: Recovery, Util. Environ. Eff., 32, 628–636, 2010.
• J. Hong, Q Wang and Z. Fan, “Synthesis of multiblock polymer containing narrow polydispersity blocks”, Macromol. Rapid Commun., 27, 57-62, 2006.
• B. Hazer, “Chemical modification of synthetic and biosynthetic polymers”, Biopolymers, 10 (6), 181-208, 2003.
• C. Cheng, E. Khoshdel, and K. L. Wooley, “One-pot tandem synthesis of a core –Shell brush copolymer from small molecule reactants by ring-opening metathesis and reversible addition-fragmentation chain transfer (co)polymerizations”, Macromolecules, 4, 2289-2292, 2007.
• B. Çakmaklı, B. Hazer, I. O.Tekin, Ş. Açıkgöz and M. Can, “Polymeric linoleic acid polyolefin conjugates: Cell adhesion and biocompatibility”, J Am Oil Chem. Soc., 84, 73-81, 2007.
• A. Allı, and B. Hazer, “Synthesis and Characterization of Poly (N-isopropyl acryl amide)-g-Poly(Linoleic Acid) / Poly(Linolenic Acid) Graft Copolymers”, J. Amer. Oil. Chem. Soc., 88, 255–263, 2011.
• H. Çulcu, M. Gökçen, A. Allı and S. Allı, “Current-voltage characteristics of Au/PLiMMA/n-Si diode under ultraviolet irradiation”, Journal of Physics and Chemistry of Solids, 103, 197–200, 2017.
• H. Çulcu, A. Allı, S. Allı and M. Gökçen, “Synthesis and characterization of poly (linoleic acid)-g-poly (methyl methacrylate) graft copolymer with applying in Au/PLiMMA/n-Si diode”, Materials Science in Semiconductor Processing, 31, 639–643, 2015.
• M. Yasan, M. Gökçen, A. Allı and S. Allı, “Electrical characterization of Au/poly (linoleic acid)-g-poly(methyl methacrylate) (PLiMMA)/n-Si diode in dark and under illumination”, Current Applied Physics, 15, 14-17, 2015.
• M. Galia, L.M. de Espinosa, J. C.Ronda,G. Lligadas and V. Cadiz, “Vegetable oil-based thermosetting polymers”, Eur. J. Lipid Sci. Technol., 112, 87–96, 2010.
• F. K. Li and R. C. Larock, “Synthesis, Structure and Properties of New Tung oil-styrene-divinylbenzene copolymers prepared by thermal polymerization”, Biomacromolecules, 4,1018–1025, 2003.
• F. Li and R. C. Larock, “Synthesis, Properties and Potential Applications of Novel Thermosetting Biopolymers from Soybean and Other Natural Oils”, in Natural Fibers, Biopolymers and Biocomposites, ed. A. K. Mohanty, M. Misra and L. T. Drzal, CRC Press, Boca Raton, FL, 2005, pp. 727–750.
• S. N. Khot , J. J. Lascala and et .all, “Development and application of triglyceridebased polymers and composites” J. Appl. Polym. Sci., 82, 703–723, 2001.
• Rybak A., Fokou P. A. and Meier M. A. R. “Metathesis as a versatile tool in oleochemistry”, Eur. J. Lipid Sci. Technol., 110, 797–804, 2008.
• P. H.Henna and R. C. Larock “Rubbery thermosets by ring-opening metathesis polymerization of a functionalized castor oil and cyclooctene”, Macromol. Mater. Eng., 292,1201–1209, 2007.
• B. Hazer, “Chemical modification of synthetic and biosynthetic polymers”, Biopolymers, 10(6), 181-208, 2003.
• B. Hazer, R. W. Lenz , Ç. Çakmaklı, M. Borcaklı and H. Koçer , “Preparation of poly(ethylene glycol) grafted poly(3-hydroxylalkanoate)s”, Macromol.Chem.Phys., 200: 903-1907, 1999.
• B. Hazer, S. İ. Demirel, M. Borcakli, M. S. Eroglu, M.Cakmak and B. Erman, “Free radical crosslinking of unsaturated bacterial polyester obtained from soybean oily acids Polymer Bulletin, 46: 389-394, 2001.
• J. O. Iroh “Poly-e-caprolactone”, Polymer Data Handbook, Mark J E (ed.) Oxford University Press, USA, 361-362, 1999.
• V. Guarino, F. Causa, P. Taddei, M. Foggia, G. Ciapetti, D. Martini, C. Fagnano , N. Baldini and L. Ambrosio, “Polylactic acid fibre-reinforced polycaprolactone scaffolds for bone tissue engineering”, Biomaterials, 29: 3662– 3670, 2008.