Synthesis and Characterization of Poly(linoleic acid)-g-poly(Nisopropylacrylamide)-g-poly (D, L-lactide) Graft Copolymers by Onepot Polymerization Method

Year 2018, , 1321 - 1334, 01.08.2018

Sema Allı , Pinar Geçit Murat Gürel , Abdulkadir Allı

https://doi.org/10.29130/dubited.434025

Cited By: 1

Abstract

In this study, one-pot three-block graft copolymers were synthesized using a combination of ring opening polymerization and free radical polymerization of Auto-oxidized polymeric linoleic acid peroxide (PLina). Graft copolymers with poly(linoleic acid)-g-poly(N-isopropylacrylamide)-g-poly(D,L-lactide) structure were synthesized the free radical polymerization with N-isopropylacrylamide (NIPAM) in monomer the main chain of PLina and the ring opening polymerization of the D, L-lactide (LA) monomer with carboxylic acid groups of PLina with together. The basic parameters such as polymerization time, initiator concentration and monomer concentration affecting the one-pot polymerization reaction were investigated. Characterization of the obtained graft copolymers were carried out using 1H NMR and GPC techniques.

Keywords

Autooxidation, ε-caprolacton, D,L-lactid, N-isopropilacrylamide, Linoleic acid, Auto-oxidation, One-step (one-pot) polymerization

One-pot PolimerleşmeYöntemiyle Poli(linoleik asit)-g-Poli(N-isopropilakrilamit)-g-Poli(D,L-laktid) Graft Kopolimerlerin Sentezi ve Karakterizasyonu

Abstract

Bu
çalışmada, Otookside polimerik linoleik asit peroksit (PLina)’nın halka açılma
polimerizasyonu ve serbest radikal polimerizasyonu bir arada kullanılarak tek
adımda (one-pot) üç bloklu graft kopolimerler sentezlendi. Poli(linoleik asit)-g-poli(N-isopropilakrilamit)-g-poli(D,L-laktid) yapısına sahip graft kopolimerler; PLina’nın ana
zincirinde bulunan peroksit grupları ile N-isopropilakrilamit
(NIPAM) monomeriyle serbest radikal polimerizasyonu ve PLina’nın karboksilik
asit grupları ile D,L-laktid (LA) monomeri arasındaki halka açılma
polimerizasyonunun bir arada (one-pot) kullanılmasıyla sentezlendiler. One-pot polimerizasyon
reaksiyonuna etki eden polimerizasyon süresi, başlatıcı konsantrasyonu ve
monomer konsantrasyonu gibi temel parametreler incelendi. Elde edilen graft
kopolimerlerin karakterizasyonları ¹H NMR ve GPC teknikleri
kullanılarak yapıldı. 

Keywords

ε-kaprolakton, N-izopropilakrilamit, D, L-laktid, Linoleik asit, Linolenik asit, Otooksidasyon, Tek adım(one-pot) polimerizasyonu

References

• M. M. Reddy, S. Vivekannandhan, M. Misra, K. S. Bhatia and K. A. Mohanty Biobased, “plastics and bionanocomposites: Current statuse and future opportunities”, Progress in Polymer Science, 38, 1653-1689, 2013.
• G. Lligadas, J. C. Ronda, M. Galia and V. Cadiz, “Renewable polymeric materials from vegetable oils: a perspective” Materials Today, 9, 2013.
• W. B. Chieng, N. A. İbrahim, Y. Y. Then and Y. Y. Loo, “Epoxidized Vegetable Oils Plasticized Poly(lactic acid) Biocomposites: Mechanical, Thermal and Morphology Properties”, Molecules, 19, 16024-10638, 2014.
• M. W. Gramlich, M. L. Robertson, and M. A. Hillmyer, “Reactive Compatibilization of Poly( L-lactid) and Conjugated Soybean Oil”, Macromolecules, 43, 2313-2321, 2010.
• E. Kılıçay, B. Çakmaklı, B. Hazer, B. E. Denkbaş and B. Açıkgöz, “Acetylsalicylic(Acid Loading and Release Studies of the PMMA-g-Polymeric Oils/Oily Acids Micro and Nanospheres”, Journal of Applied Polymer Science, 3, 1610-1618, 2010.
• B. Çakmaklı, B. Hazer, I. O. Tekin, S. Kızgut, M. Köksal, and Y. Menceloğlu, “Synthesis and characterization of polymeric linseed oil grafted methyl methacrylate or styrene”, Macromol. Biosci., 4, 649-655, 2004.
• B. Çakmaklı, B. Hazer, . O. Tekin and F. B. Cömert, “Synthesis and characterization of polymeric soybean oil-g-methyl methacrylate (and n-butyl methacrylate) grafted copolymers: Biocompatibility and bacterial adhesion”, Biomacromolecules, 6, 1750-1758, 2005.
• E. Keleş and B. Hazer, “Autooxidized Polyunsaturated Oil/Oily Acids: Post-it Application and Reaction with Fe(III) and Adhesion Properties” Macromolecular Symposia, 269,154-160, 2008.
• A. Allı, and B Hazer, “Poly(N-isopropylacrylamide) thermoresponsive cross-linked conjugates containing polymeric soybean oil and/or polypropylene glycol”, Eur. Polym. Jour., 44, 1701-1713, 2008.
• A. Allı, T. Şanal, B. Hazer, “Redox polymerization of N-isopropylacrylamide by using hydroxylated soya oil polymer”, Tur. Jour. Chem., 39, 382-394, 2015.
• E. Kılıçay, B. Çakmaklı, B. Hazer, E. B. Denkbas, and B. Açıkgöz, “Acetylsalicylic acid loading and release studies of the PMMA-g-Poymeric oils/oily acids micro and nanospheres”, Journal of Applied Polymer Science, 119(3), 1610-1618, 2011.
• A. Allı, S. Allı, C. R. Becer and B. Hazer, “One-pot synthesis of poly(linoleic acid)-g-poly (styrene)-g-poly(ε-caprolactone) graft copolymers”, J. Amer. Oil Chem. Soc. (JAOCS), 91, 849–858, 2014.
• S. Allı, R. S. Aydın Tığlı,, A. Allı and B. Hazer, “Biodegradable Poly(ε-Caprolactone)- Based Graft Copolymers:Via Poly(Linoleic Acid): In Vitro Enzymatic Evaluation”, J. Amer. Oil. Chem. Soc., 92, 449-458, 2015.
• A. Allı, S. Allı, C. R. Becer and B. Hazer, “Nitroxide mediated copolymerization of styrene and pentafluorostyrene initiated by polymeric linoleic acid”, European Journal of Lipid Science and Technology, 118 (2), 279-287, 2016.
• A. Allı, Y. Arı and M. Gökçen, “Novel Poly(linolenic acid) Graft Copolymers: Synthesis, Characterization and Electrical Properties”, J. Am. Oil Chem. Soc., 93, 895–904, 2016.
• T. Öztürk, M. Göktaş and B. Hazer, “One-Step Synthesis of Triarm Block Copolymers via Simultaneous Reversible-Addition Fragmentation Chain Transfer and Ring- Opening Polymerization”, J. Appl. Polym. Sci., 117, 1638–1645, 2010.
• T. Öztürk, and İ. Cakmak ,“One-step synthesis of multiphase block copolymers via simultaneus free radical and ring opening polymerization using poly(ethylene oxide) possessing azo group”, J Macromol. Sci. Part A Pure and Appl. Chem., 45, 572–577. 2008.
• M. Le Hellaye, C. Lefay, T.P. Davis, M. H. Stenzel and C. J. Barner-Kowollik. “Simultaneous reversible addition fragmentation chain transfer and ring-opening polymerization”,. J. Polym. Sci. Part A. Polym. Chem., 46: 3058-3067, 2008.
• Y. C. Yu, G. Li, H. U. Kang and J. U. Youk , “One-step synthesis of poly(alkyl methacrylate)-b-polyester block copolymers via a dual initiator route combining RAFT polymerization and ROP”, Coll. Polym. Sci., 290: 1707-1712, 2012.
• M. K. Mahanthappa, F. S. Bates and M. A. Hillmyer, “ Synthesis of ABA triblock copolymers by a tandem ROMP-RAFT strategy”, Macromolecules, 38:7890-7894, 2005.
• H. Mori, S. Masuda and T. Endo, “Ring-opening copolymerization of 10-methylene-9,10 dihydroanthryl-9-spirophenylcyclopropane via free radical and RAFT processes”, Macromolecules, 41: 632–639, 2008.
• D. H Han and C. Y. Pan, , “ Preparation and characterization of heteroarm H-shaped Terpolymers by combination of reversible addition-fragmentation transfer polymerization and ring-opening polymerization”, J. Polym. Sci. Part A Polym. Chem., 45, 789-799, 2007.
• X. W. Xu and J. L. Huang, “Synthesis and characterization of amphiphilic copolymer of linear poly(ethylene oxide) linked with [poly(styrene-co-2-hydroxyethyl methacrylate)-graft-poly(epsilon-caprolactone)] using sequential controlled polymerization”, J. Polym. Sci. Part A. Polym. Chem., 44: 467-476, 2006.
• J. Liu and C. Y. Pan, Synthesis and characterization of H-shaped copolymers by combination of RAFT polymerization and CROP”, Polymer, 46, 11133-11141, 2005.
• J. Hong, Q. Wang, and Z. Fan, “Synthesis of multiblock polymer containing narrow polydispersity blocks”, Macromol. Rapid Commun., 27, 57-62, 2006.
• 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.
• Y. You, C. Hong, W. Wang, W. Lu, and C. Y. Pan, “Preparation and characterization of thermally esponsive and biodegradable block copolymer comprised of PNIPAAM and PLA by combination of ROP and RAFT methods”, Macromolecules, 37, 9761-9797, 2004.
• C. Chang, H. Wei, C. Y. Quan, Y. Y. Li, J. L iu, Z. C. Wang, S. X. Cheng, X. Z. Zhang, R. X. Zhuo, “Fabrication of thermosensitive PCL-PNIPAAm-PCL triblock copolymeric micelles for drug delivery”, J. Polym. Sci. Part A Polym. Chem. 46, 3048-3057, 2008.
• P. J. Shi, Y. G. Li and C .Y. Pan, “Block and star block copolymers by mechanism transformation-X.Synthesis of poly(ethylene oxide) methyl ether/polystyrene/poly(L-lactide) ABC miktoarm star copolymers of by combination of RAFT and ROP”, Eur. Polym. J., 40, 1283-1290, 2004.
• B. Luan, B. Q. Zhang, C. Y. Pan, “Synthesis and characterizations of well-defined branched polymers with AB(2) branches by combination of RAFT polymerization and ROP as well as ATRP”, J. Polym. Sci. Part A Polym. Chem., 44, 549-560, 2006.