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Journal of Polymers and the Environment

, Volume 27, Issue 11, pp 2562–2576 | Cite as

Autoxidized Oleic Acid Bifunctional Macro Peroxide Initiators for Free Radical and Condensation Polymerization. Synthesis and Characterization of Multiblock Copolymers

  • Baki HazerEmail author
  • Elif Ayyıldız
  • Melike Eren
  • Hale Seçilmiş Canbay
  • Richard D. AshbyEmail author
Original paper
  • 57 Downloads

Abstract

Autoxidation of unsaturated fatty acids gives fatty acid macroperoxide initiators containing two functionalities which can lead to free radical and condensation polymerizations in a single pot. The oleic acid macroperoxide initiator obtained by ecofriendly autoxidation (Pole4m) was used in both the free radical polymerization of styrene and the condensation polymerization with amine-terminated polyethylene glycol (PEGNH2) to obtain triblock branched graft copolymers. The narrow molar masses of the poly oleic acid-g-styrene (PoleS) and poly oleic acid-g-styrene-g-PEG (PoSG) graft copolymers were successfully obtained. The inclusion of oleic acid decreased the glass transition temperature of the polystyrene segment because of the plasticizing effect of oleic acid. In addition, a mechanical property of the copolymer was improved when compared with the pure PS. Structural characterization, morphology of the fracture surface, micelle formation, thermal analysis and molar masses of the obtained products were also evaluated.

Keywords

Oleic acid Macroperoxide initiator Autoxidation Amphiphilic copolymer 

Notes

Acknowledgements

This work was supported by the Kapadokya University Research Fund (KÜN.2018-BAGP-001) and Bülent Ecevit University Research Fund (#BEU-2017-72118496-01). The Authors thank to Koray Alper and Fatih Pekdemir for taking SEM and FTIR spectra, respectively. The Authors thank to Serdar Çoban, Sıdıka Saraç Tabaklı and Gülşen Darıcı (Cilas Kauçuk, Devrek, Zonguldak, Turkey) for taking stress–strain measurements.

Compliance with Ethical Standards

Conflict of interest

There is not any conflict of interest.

References

  1. 1.
    Reddy MM, Vivekanandhan S, Misra M, Bhatia SK, Mohanty K (2013) Biobased plastics and bio nanocomposites: Current status and future opportunities. Prog Polym Sci 38:1653–1689Google Scholar
  2. 2.
    Miyaji H, Satoh K, Kamigaito M (2016) Bio-based polyketones by selective ring-opening radical polymerization of a-pinene-derived pinocarvone. Angew Chem Int Ed 55:1372–1376Google Scholar
  3. 3.
    Sudesh K, Iwata T (2008) Sustainability of biobased and biodegradable plastics. CLEAN 36:433–442Google Scholar
  4. 4.
    Shimada K, Fujikawa K, Yahara K, Nakamura T (1992) Antioxidative properties of xanthan on the autoxidation of soybean oil in cyclodextrin emulsion. J Agric Food Chem 40:945–948Google Scholar
  5. 5.
    Khan S, Wang Z, Wang R, Zhang L (2016) Synthesis and structure design of new bio-based elastomers via Thiol-ene-Click Reactions. Mater Sci Eng C 67:554–560Google Scholar
  6. 6.
    Miao S, Wang P, Su Z, Zhang S (2014) Vegetable-oil-based polymers as future polymeric biomaterials. Acta Biomater 10:1692–1704PubMedGoogle Scholar
  7. 7.
    Guner FS, Yagci Y, Erciyes AT (2006) Polymers from triglyceride oils. Prog Polym Sci 31:633–670Google Scholar
  8. 8.
    Sharma BK, Adhvaryu A, Erhan S (2006) Synthesis of hydroxy thio-ether derivatives of vegetable oil. J Agric Food Chem 54:9866–9872PubMedGoogle Scholar
  9. 9.
    Wang Z, Zhang X, Wang R, Kang H, Qiao B, Ma J, Zhang L, Wang H (2012) Synthesis and characterization of novel soybean-oil-based elastomers with favorable processability and tunable properties. Macromolecules 45:9010–9019Google Scholar
  10. 10.
    Hazer DB, Hazer B (2009) Kaymaz F (2009) Synthesis of microbial elastomers based on soybean oily acids. Biocompat Stud Biomed Mater 4:035011Google Scholar
  11. 11.
    Petrović ZS, Zhang W, Javni J (2005) Structure and properties of polyurethanes prepared from triglyceride polyols by ozonolysis. Biomacromol 6:713–719Google Scholar
  12. 12.
    Narine SS, Kong XH, Bouzidi L, Sporns P (2007) Physical properties of polyurethanes produced from polyols from seed oils: I. Elastomers. J Am Oil Chem Soc 84:55–63Google Scholar
  13. 13.
    Porter NA (2013) A perspective on free radical autoxidation: the physical organic chemistry of polyunsaturated fatty acid and sterol peroxidation. J Org Chem 78:3511–3524PubMedPubMedCentralGoogle Scholar
  14. 14.
    Soucek MD, Khattab T, Wu J (2012) Review of autoxidation and driers. Prog Org Coat 73:435–454Google Scholar
  15. 15.
    Hamalainen TI, Sundberg S, Makinen M, Kaltia S, Hase T, Hopia A (2001) Hydroperoxide formation during autoxidation of conjugated linoleic acid methyl ester. Eur J Lipid Sci Technol 103:588–593Google Scholar
  16. 16.
    Yin H, Xu L, Porter NA (2011) Free radical lipid peroxidation: Mechanisms and analysis. Chem Rev 111:5944–5972Google Scholar
  17. 17.
    Choe E, Min DB (2006) Mechanisms and factors for edible oil oxidation. Compr Food Sci Food Saf 5:169–186Google Scholar
  18. 18.
    Mcclements DJ, Decker EA (2000) Lipid oxidation in oil-in-water emulsions: Impact of molecular environment on chemical reactions in heterogeneous food systems. J Food Sci 65:1270–1282Google Scholar
  19. 19.
    Köckritz A, Martin A (2008) Oxidation of unsaturated fatty acid derivatives and vegetable oils. Eur J Lipid Sci Technol 110:812–824Google Scholar
  20. 20.
    Ionescu M, Petrović ZS, Wan X (2007) Ethoxylated soybean polyols for polyurethanes. J Polym Environ 15:237–243Google Scholar
  21. 21.
    Fornof AR, Onah E, Ghosh S, Frazier CE, Sohn S, Wilkes GL, Long TE (2006) Synthesis and characterization of triglyceride-based polyols and tack-free coatings via the air oxidation of soy oil. J Appl Polym Sci 102:690–697Google Scholar
  22. 22.
    Montero de Espinosa L, Ronda JC, Galia M, Cadiz VA (2009) New route to acrylate oils: Crosslinking and properties of acrylate triglycerides from high oleic sunflower oil. J Polym Sci A 47:1159–1167Google Scholar
  23. 23.
    Keleş E, Hazer B (2009) Synthesis of segmented polyurethane based on polymeric soybean oil polyol and poly (ethylene glycol). J Polym Environ 17:153–158Google Scholar
  24. 24.
    Acar M, Çoban S, Hazer B (2013) Novel water soluble soya oil polymer from oxidized soya oil polymer and diethanol amine. J Macromol Sci A 50:287–296Google Scholar
  25. 25.
    Hazer B, Akyol E (2016) Efficiency of gold nano particles on the autoxidized soybean oil polymer. Fractionation and structural analysis. J Amer Oil Chem Soc 93:201–213Google Scholar
  26. 26.
    Hazer B, Kalaycı ÖA (2017) High fluorescence emission silver nano particles coated with poly (styrene-g-soybean oil) graft copolymers: antibacterial activity and polymerization kinetics. Mater Sci Eng C 74:259–269Google Scholar
  27. 27.
    Yıldız U, Hazer B, Tauer K (2012) Tailoring Polymer Architectures with Macromonomer azoinitiators. Polym Chem 3:1107–1118Google Scholar
  28. 28.
    Erciyes AT, Erim M, Hazer B, Yağcı Y (1992) Synthesis of polyacrylamide flocculants with PEG segments by redox polymerization. Angew Macromol Chem 200:163–171Google Scholar
  29. 29.
    Yıldız U, Hazer B (2000) Dispersion redox copolymerization of methyl methacrylate with macromonomeric azoinitiator as a macrocrosslinker. Polymer 41:539–544Google Scholar
  30. 30.
    Hazer B (1987) Polymerization of vinyl monomers by a new oligoperoxide. Oligo (adipoyl 5- peroxy 2,5- dimethyl n-hexyl) peroxide. J Polym Sci Polym Chem Ed 25:3349–3354Google Scholar
  31. 31.
    Öztürk T, Yılmaz SS, Hazer B (2008) Synthesis of a new macroperoxy initiator with methyl methacrylate and t-butyl peroxy ester by atom transfer radical polymerization and copolymerization with conventional vinyl monomers. J Macromol Sci Part A 45:811–820Google Scholar
  32. 32.
    İnce Ö, Akyol E, Sulu E, Şanal T, Hazer B (2016) Synthesis and characterization of novel rod-coil (tadpole) poly(linoleic acid) based graft copolymers. J Polym Res 23:1–10Google Scholar
  33. 33.
    Allı A, Allı S, Becer CR, Hazer B (2016) Nitroxide mediated copolymerization of styrene and pentafluorostyrene initiated by polymeric linoleic acid. Eur J Lipid Sci Tech 118:279–287Google Scholar
  34. 34.
    Hazer B, Ayyıldız E, Bahadır F (2017) Synthesis of PNIPAM-PEG double hydrophilic polymers using oleic acid macro peroxide initiator. J Am Oil Chem Soc 94:1141–1151Google Scholar
  35. 35.
    Hazer B (2010) Amphiphilic poly (3-hydroxy alkanoate)s: potential candidates for medical applications. Int J Polym Sci.  https://doi.org/10.1155/2010/423460 CrossRefGoogle Scholar
  36. 36.
    Hutanu D, Frishberg MD, Guo L, Darie CC (2014) Recent applications of polyethylene glycols (pegs) and peg derivatives. Modern Chem Appl 2:132.  https://doi.org/10.4172/2329-6798.1000132 CrossRefGoogle Scholar
  37. 37.
    Hazer DB, Mut M, Dinçer N, Sarıbaş Z, Hazer B, Özgen T (2012) The efficacy of Ag embedded pp-g-peg coated ventricular catheters on prevention of shunt catheter infection in rats. Childs Nerv Syst 28:839–846PubMedGoogle Scholar
  38. 38.
    Hazer B (1995) Grafting on polybutadiene with macro or macromonomer initiator containing poly(ethylene glycol) units. Macromol Chem Phys 196:1945–1952Google Scholar
  39. 39.
    Townsend KJ, Busse K, Kressler J, Scholz C (2005) Contact angle, WAXS, and SAXS analysis of poly(β-hydroxybutyrate) and poly(ethylene glycol) block copolymers obtained via Azotobacter vinelandii UWD. Biotechnol Prog 21:959–964PubMedGoogle Scholar
  40. 40.
    Charoongchit P, Suksiriworapong J, Sripha K, Mao S, Sapin-Minet A, Maincent P, Junyaprasert VB (2017) Self-aggregation of cationically modified poly(ε-caprolactone)2-co-poly(ethylene glycol) copolymers: Effect of cationic grafting ligand and poly(ε-caprolactone) chain length. Mater Sci Eng C 72:444–455Google Scholar
  41. 41.
    Gody G, Rossner C, Moraes J, Vana P, Maschmeyer T, Perrier S (2012) One-pot RAFT/“click” chemistry via isocyanates: efficient synthesis of α-end-functionalized polymers. J Am Chem Soc 134:12596–12603PubMedGoogle Scholar
  42. 42.
    Wang S, Fu C, Zhang Y, Tao L, Li S, Wei Y (2012) One-pot cascade synthetic strategy: a smart combination of chemo enzymatic transesterification and raft polymerization. ACS Macro Lett 1:1224–1227Google Scholar
  43. 43.
    Geng J, Lindqvist J, Mantovani G, Haddleton DM (2008) Simultaneous copper(i)-catalyzed azide–alkyne cycloaddition (cuaac) and living radical polymerization. Angew Chem Int Ed 47:4180–4183Google Scholar
  44. 44.
    Yagci Y (1985) Block copolymers by combinations of cationic and radical radical routes. 1. A new difunctional azo-oxocarbenium initiator for cationic polymerization. Polym Commun 26:7–8Google Scholar
  45. 45.
    Hazer B (1991) Synthesis of tetrahydrofuran-styrene (or methyl methacrylate) block copolymers via cationic to radical transformation process. Eur Polym J 27:775–777Google Scholar
  46. 46.
    Hazer B (1990) Cationic polymerization of tetrahydrofuran initiated by difunctional initiators. Synthesis of block copolymers. Eur Polym J 26:1167–1170Google Scholar
  47. 47.
    Hazer B (1991) Synthesis of styrene-tetrahydrofuran branched block copolymers. Eur Polym J 27:975–978Google Scholar
  48. 48.
    Mazurowski M, Gallei M, Li J, Didzoleit H, Stühn B, Rehahn M (2012) Redox-responsive polymer brushes grafted from polystyrene nanoparticles by means of surface-initiated atom transfer radical polymerization. Macromolecules 45:8970–8981Google Scholar
  49. 49.
    Díaz I, Langston P, Ovejero G, Romero MD, Díez E (2010) Purification process design in the production of styrene monomer. Chem Eng Process 49:367–375Google Scholar
  50. 50.
    Firestone D (1994) Determination of the iodine value of oils and fats: summary of collaborative study. JAOAC Int 77:674–676Google Scholar
  51. 51.
    Brimberg UI, Kamal-Eldin A (2003) On the kinetics of the autoxidation of fats: substrates with conjugated double bonds. Eur J Lipid Sci Technol 105:17–22Google Scholar
  52. 52.
    Porter NA, Mills KA, Carter RL (1994) A mechanistic study of oleate autoxidation: competing peroxyl h-atom abstraction and rearrangement. J Am Chem Soc 116:6690–6696Google Scholar
  53. 53.
    Knothe G, Kenar JA (2004) Determination of the fatty acid profile by 1H-NMR spectroscopy. Eur J Lipid Sci Technol 106:88–96Google Scholar
  54. 54.
    Guillén MD, Ruiz A (2005) Study by proton nuclear magnetic resonance of the thermal oxidation of oils rich in oleic acyl groups. J Am Oil Chem Soc 82:349–355Google Scholar
  55. 55.
    Hwang H-S, Doll KM, Winkler-Moser JK, Vermillion K, Liu SX (2013) No evidence found for diels–alder reaction products in soybean oil oxidized at the frying temperature by NMR study. J Am Oil Chem Soc 90:825–834Google Scholar
  56. 56.
    Matyjaszewski K, Spanswick J (2005) Controlled/living radical polymerization. Mater Today 8:26–33Google Scholar
  57. 57.
    Hazer B (1996) Poly(beta-hydroxynonanoate) and polystyrene or poly(methyl methacrylate) graft copolymers: microstructure characteristics and mechanical and thermal behavior. Macromol Chem Phys 197:431–441Google Scholar
  58. 58.
    Cakmakli B, Hazer B, Borcakli M (2001) Poly(styrene peroxide) and poly(methyl methacrylate peroxide) for grafting on unsaturated bacterial polyesters. Macromol Biosci 1:348–354Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Aircraft Airframe Engine MaintenanceKapadokya UniversityÜrgüp, NevşehirTurkey
  2. 2.Department of Chemistry, Faculty of Engineering, Faculty of Arts and SciencesBülent Ecevit UniversityZonguldakTurkey
  3. 3.Department of Nano Technology Engineering, Faculty of EngineeringBülent Ecevit UniversityZonguldakTurkey
  4. 4.Bioengineering DepartmentMehmet Akif Ersoy UniversityBurdurTurkey
  5. 5.USDA ARSWyndmoorUSA

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