KaydedilenlerDerginizi ekleyin

Dergiler / Gazi Üniversitesi Mühendislik Mimarlık Fakültesi Dergisi / 2026 / Cilt: 41 Sayı: 1

Mikrodalga destekli halka-açılma polimerizasyonu ile Zn(Oct)2 katalizörü varlığında PLA-PEG-PLA üçlü-blok kopolimerlerinin sentezi

Synthesis and characterization of microwave-assisted ring-opening polymerization of PLA-PEG-PLA triblock copolymers in the presence of Zn(Oct)2 catalyst

Seher Şenada Karabulut(İSTANBUL ÜNİVERSİTESİ-CERRAHPAŞA, MÜHENDİSLİK FAKÜLTESİ, KİMYA MÜHENDİSLİĞİ BÖLÜMÜ)0009-0000-3548-3012
Serdar Bayyar(CHT TURKEY Kimya)0009-0001-9722-4443
Esra Okur(CHT TURKEY Kimya)0009-0006-9835-1694
Ayça Müftüler(İSTANBUL ÜNİVERSİTESİ-CERRAHPAŞA, MÜHENDİSLİK FAKÜLTESİ, KİMYA MÜHENDİSLİĞİ BÖLÜMÜ)0000-0003-3183-3729
Hüseyin Deligöz(Istanbul University-Cerrahpasa)0000-0002-0915-2911
Sayfa
17–28
Yayın Tarihi
2026-02-19
🏛️Bu makalenin bibliyografik verileri ve tam metin bağlantısı DergiPark üzerinden sağlanmıştır.
DergiPark Kaydı ↗
✨

Yapay Zeka Hızlı Bakış & Çıkarımlar

AI Insight
⚡ TL;DR(1 Cümlede Hızlı Çıkarım)

FTIR, DSC, 1H-NMR, GC-MS ve GPC analizleri sonucunda %0,6 oranında Zn(Oct)2 varlığında sentezlenen ürünlerin, düşük polidispersite indeksi (PDI) (1,54), yüksek dönüşüm oranı (%99,5), homojen moleküler yapı (Mn=5.642 g/mol, Mw=8.685 g/mol), düşük camsı geçiş sıcaklığı (Tg:–19,9 °C) ve erime sıcaklığı (Te:64,3°C) ile en kontrollü yapıya sahip kopolimerleri verdiğini ortaya koymuştur.

📌 3 Maddede Bu Makale

🎯
Amaç & Hipotez:Polietilen glikol (PEG) ve poli(L-laktik asit) (PLA) esaslı üçlü-blok kopolimerler, biyobozunur ve biyouyumlu özellikleri nedeniyle biyomedikal ve teknik tekstil uygulamalarında büyük ilgi görmektedir.
📊
Temel Bulgular & Veri:Bu çalışmada, PLA-PEG-PLA üçlü-blok kopolimerleri mikrodalga destekli halka-açılma polimerizasyonu (mROP) yöntemi ile çinko oktoat (Zn(Oct)2) katalizörü varlığında sentezlenmiştir.
💡
Sonuç & Katkı:FTIR, DSC, 1H-NMR, GC-MS ve GPC analizleri sonucunda %0,6 oranında Zn(Oct)2 varlığında sentezlenen ürünlerin, düşük polidispersite indeksi (PDI) (1,54), yüksek dönüşüm oranı (%99,5), homojen moleküler yapı (Mn=5.642 g/mol, Mw=8.685 g/mol), düşük camsı geçiş sıcaklığı (Tg:–19,9 °C) ve erime sıcaklığı (Te:64,3°C) ile en kontrollü yapıya sahip kopolimerleri verdiğini ortaya koymuştur.
🔬Tür:Deneysel Tarla Denemesi
📍Kapsam:Genişletilmiş Akademik Örneklem
⚙️Değişkenler:Poli(L-laktik asit) · Polietilen glikol · Zn(Oct)2

Özet

Polietilen glikol (PEG) ve poli(L-laktik asit) (PLA) esaslı üçlü-blok kopolimerler, biyobozunur ve biyouyumlu özellikleri nedeniyle biyomedikal ve teknik tekstil uygulamalarında büyük ilgi görmektedir. Bu çalışmada, PLA-PEG-PLA üçlü-blok kopolimerleri mikrodalga destekli halka-açılma polimerizasyonu (mROP) yöntemi ile çinko oktoat (Zn(Oct)2) katalizörü varlığında sentezlenmiştir. Monomer besleme oranı sabit tutularak (ağırlıkça LA/PEG=70:30), farklı Zn(Oct)2 katalizör miktarlarının (ağırlıkça %0,2; %0,4; %0,6; %3 ve %6) sentezlenen polimerlerin yapısal, termal ve fizikokimyasal özellikleri üzerindeki etkileri araştırılmıştır. FTIR, DSC, 1H-NMR, GC-MS ve GPC analizleri sonucunda %0,6 oranında Zn(Oct)2 varlığında sentezlenen ürünlerin, düşük polidispersite indeksi (PDI) (1,54), yüksek dönüşüm oranı (%99,5), homojen moleküler yapı (Mn=5.642 g/mol, Mw=8.685 g/mol), düşük camsı geçiş sıcaklığı (Tg:–19,9 °C) ve erime sıcaklığı (Te:64,3°C) ile en kontrollü yapıya sahip kopolimerleri verdiğini ortaya koymuştur. Literatürde yer alan çalışmalardan farklı olarak, mikrodalga destekli halka-açılma polimerizasyonu ile PLA-PEG-PLA kopolimerlerinin sentezlenmesinde farklı miktarlarda Zn(Oct)2 (%0,2-%6,0) kullanımının sistematik olarak polimerizasyon süresi, dönüşüm, moleküler ağırlık dağılımı ve PDI gibi özellikler üzerindeki etkileri detaylı olarak incelenmiştir. Bu yönüyle çalışma, hem mikrodalga sisteminin konvensiyonel üretim yöntemleri üzerindeki avantajını, hem de Zn(Oct)2 katalizörünün mevcutta kullanılan Sn(Oct)2’a göre düşük toksisite ve yüksek kontrollü zincir oluşumu potansiyelini açıkça göstermiştir.

Abstract

Polyethylene glycol (PEG) and poly(L-lactic acid) (PLA)-based triblock copolymers have attracted significant attention for biomedical and technical textile applications due to their biodegradable and biocompatible properties. In this study, PLA–PEG–PLA triblock copolymers were synthesized via microwave-assisted ring-opening polymerization (mROP) in the presence of zinc octoate (Zn(Oct)2) catalyst. While maintaining a constant monomer feed ratio (LA/PEG = 70:30 w/w), the effects of various Zn(Oct)2 catalyst amounts (0.2, 0.4, 0.6, 3.0 and 6.0 wt%) on the structural, thermal, and physicochemical properties of the synthesized polymers were systematically investigated. Analytical techniques including FTIR, DSC, 1H NMR, GC-MS, and GPC analyses revealed that copolymers synthesized with 0.6 wt% Zn(Oct)2 exhibited the most controlled structure, characterized by a low polydispersity index (PDI) (1.54), high conversion rate (99.5%), homogeneous molecular structure (Mn = 5.642 g/mol, Mw = 8.685 g/mol), low glass transition temperature (Tg = –19.9 °C), and a distinct melting temperature (Tm = 64.3 °C). Unlike the studies reported in the literature, the present work systematically examined the effects of using different amounts of Zn(Oct)2 concentrations (0.2–6.0 wt%) on properties such as polymerization time, conversion, molecular weight distribution, and PDI in the microwave-assisted ring-opening polymerization of PLA-PEG-PLA copolymers. In this respect, the study clearly demonstrated both the advantage of the microwave system over conventional production methods and the low toxicity and high controlled chain formation potential of the Zn(Oct)2 catalyst compared to the currently used Sn(Oct)2.

🔖

Bu Makaleye Atıf Yap

Karabulut, S. Ş., Bayyar, S., Okur, E., Müftüler, A., Deligöz, H. (2026). Mikrodalga destekli halka-açılma polimerizasyonu ile Zn(Oct)2 katalizörü varlığında PLA-PEG-PLA üçlü-blok kopolimerlerinin sentezi. Gazi Üniversitesi Mühendislik Mimarlık Fakültesi Dergisi, Cilt: 41 Sayı: 1, 17–28. https://doi.org/10.17341/gazimmfd.1722242

📄 Tam Metin PDF Okuyucu

📄

PDF görüntüleyici hazırlanıyor...

Kaynakça (42)

  1. Garlotta, D., A literature review of poly(lactic acid), Journal of Polymers and the Environment, 9 (2), 63–84, 2001.
  2. Uzunoğlu T., Altınten A., PMMA/PLA/Clay biodegradable nanocomposite synthesis and characterization, Journal of the Faculty of Engineering and Architecture of Gazi University, 39 (4), 2163-2175, 2024.
  3. Drumright, R. E., Gruber, P. R., Henton, D. E., Polylactic acid technology, Advanced Materials, 12 (23), 1841–1846, 2000.
  4. Jiménez, A., Peltzer, M., Ruseckaite, R., Poly(lactic acid) science and technology: processing, properties, additives and applications, Royal Society of Chemistry, No. 12, 2015.
  5. Balla, E., Daniilidis, V., Karlioti, G., Kalamas, T., Stefanidou, M., Bikiaris, N. D., Vlachopoulos, A., Koumentakou, I., & Bikiaris, D. N., Poly(lactic Acid): A Versatile Biobased Polymer for the Future with Multifunctional Properties-From Monomer Synthesis, Polymerization Techniques and Molecular Weight Increase to PLA Applications. Polymers, 13 (11), 1822, 2021.
  6. Naser, A. Z., Deiab, I., Darras, B. M., Poly (lactic acid)(PLA) and polyhydroxyalkanoates (PHAs), green alternatives to petroleum-based plastics: a review. RSC advances, 11 (28), 17151-17196, 2021.
  7. Mooney, D. J., Baldwin, D. F., Suh, N. P., Vacanti, J. P., Langer, R., Novel approach to fabricate porous sponges of poly(D,L-lactic-co-glycolic acid) without the use of organic solvents, Biomaterials, 17 (14), 1417–1422, 1996.
  8. Bendix, D., Chemical synthesis of polylactide and its copolymers for medical applications, Polymer Degradation and Stability, 59, 129–135, 1998.
  9. Yılmaz M., Yılmaz N.F., Kılıç A., Mazı H., Investigation of Manufacturability of in-situ crosslinked Polylactic Acid (PLA) and Peroxide composite in additive manufacturing method, Journal of the Faculty of Engineering and Architecture of Gazi University, 39 (2), 859-867, 2024.
  10. Bikiaris, N. D., Klonos, P. A., Christodoulou, E., Barmpalexis, P., & Kyritsis, A., Plasticization Effects of PEG of Low Molar Fraction and Molar Mass on the Molecular Dynamics and Crystallization of PLA-b-PEG-b-PLA Triblock Copolymers Envisaged for Medical Applications. The Journal of Physical Chemistry B, 129 (13), 3514-3528, 2025
  11. Alexis, F., Factors affecting the degradation and drug-release mechanism of poly(lactic acid) and poly[(lactic acid)-co-(glycolic acid)], Polymer International, 54 (1), 36–46, 2005.
  12. Arslan R., Akyol E., Dalkılıç A.S., Investigation of the usage of nano-Titanium dioxide Produced with Polyethylene glycol and Alginate additives as nanofluid, Journal of the Faculty of Engineering and Architecture of Gazi University, 40 (1), 331-341, 2025.
  13. Ergene B., Ispartalı H., Karakılınç U., Impact behavior of PET-G parts produced by fused deposition modelling depending on layer height and test temperature, Journal of the Faculty of Engineering and Architecture of Gazi University, 38 (3), 1345-1359, 2023.
  14. Jedliński, Z., Kurcok, P., Walach, W., Janeczek, H., Radecka, I., Polymerization of lactones, 17. Synthesis of ethylene glycol-L-lactide block copolymers, Die Makromolekulare Chemie: Macromolecular Chemistry and Physics, 194 (6), 1681–1689, 1993.
  15. Wan, Y., Chen, W., Yang, J., Bei, J., Wang, S., Biodegradable poly(L-lactide)-poly(ethylene glycol) multiblock copolymer: synthesis and evaluation of cell affinity, Biomaterials, 24 (13), 2195–2203, 2003.
  16. Bikiaris, N. D., Klonos, P. A., Kyritsis, A., & Barmpalexis, P., Structural and thermodynamical investigation in triblock copolymers of polylactide and poly (ethylene glycol), PLA-b-PEG-b-PLA, envisaged for medical applications. Materials Today Communications, 38, 107799, 2024.
  17. Xiao, R. Z., Zeng, Z. W., Zhou, G. L., Wang, J. J., Li, F. Z., & Wang, A. M., Recent advances in PEG–PLA block copolymer nanoparticles. International Journal of Nanomedicine, 5, 1057–1065, 2010.
  18. Kubisa P, Lapienis G, Biela T. Star-shaped copolymers with PLA–PEG arms and their potential applications as biomedical materials. Polymers for Advanced Technologies, 32, 3857–3866, 2021.
  19. Ghasemi, R., Abdollahi, M., Emamgholi Zadeh, E. et al. mPEG-PLA and PLA-PEG-PLA nanoparticles as new carriers for delivery of recombinant human Growth Hormone (rhGH). Sci Rep 8, 9854. 2018.
  20. Ding, Y., Feng, W., Lu, B., Wang, P., Wang, G., Ji, J., PLA-PEG-PLA tri-block copolymers: Effective compatibilizers for promotion of the interfacial structure and mechanical properties of PLA/PBAT blends. Polymer, 146, 179-187, 2018.
  21. Li, S., Vert, M., Synthesis, characterization, and stereocomplex-induced gelation of block copolymers prepared by ring-opening polymerization of L(D)-lactide in the presence of poly(ethylene glycol), Macromolecules, 36 (21), 8008–8014, 2003.
  22. Auras, R. A., Lim, L. T., Selke, S. E., Tsuji, H., Poly(lactic acid): Synthesis, Structures, Properties, Processing and Applications, John Wiley and Sons, 2010.
  23. Leenslag, J. W., Pennings, A. J., Synthesis of high-molecular-weight poly(L-lactide) initiated with tin 2-ethylhexanoate, Makromol. Chem., 188, 1809–1814, 1987.
  24. Libiszowski, J., Kowalski, A., Duda, A., Penczek, S., Kinetics and mechanism of cyclic esters polymerization initiated with covalent metal carboxylates, 5. End-group studies in the model ε-caprolactone and L,L-dilactide/Tin(II) and zinc octoate/butyl alcohol systems, Macromolecular Chemistry and Physics, 203 (10-11), 1694–1701, 2002.
  25. Mazarro, R., Gracia, I., Rodríguez, J. F., Storti, G., Morbidelli, M., Kinetics of the ring-opening polymerization of D,L-lactide using zinc(II) octoate as catalyst, Polymer International, 61, 265–273, 2012.
  26. Deng, X., Liu, Y., Yuan, M., Li, X., Liu, L., Jia, W. X., Preparation and characterization of poly-DL-lactide-poly(ethylene glycol) microspheres containing λDNA, Journal of Applied Polymer Science, 86 (10), 2557–2566, 2002.
  27. Tan, C. H., Ahmad, A., Anuar, F. H., Investigation of the synthesis of poly-D, L-lactide-co-poly(ethylene glycol) flexible thermoplastic, International Journal of Polymer Analysis and Characterization, 21 (2), 104–111, 2016.
  28. Wu, Y., Li, L., Chen, S. et al. Synthesis, characterization, and crystallization behaviors of poly(D-lactic acid)-based triblock copolymer. Sci Rep 10, 3627, 2020.
  29. Wang, Z. Y., Zhao, Y. M., Wang, F., Syntheses of poly(lactic acid)-poly(ethylene glycol) serial biodegradable polymer materials via direct melt polycondensation and their characterization, Journal of Applied Polymer Science, 102 (1), 577–587, 2006.
  30. Zhang, Y., Wang, X. L., Wang, Y. Z., Qu, M. H., Microwave-assisted single-step synthesis of poly(L-lactic acid)-poly(ethylene glycol) copolymers, Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 46 (6), 631–635, 2009.
  31. Li, G., Zhao, N., Bai, W., Chen, D. L., Xiong, C. D., Microwave-assisted ring-opening polymerization of poly(glycolic acid-co-lactic acid) copolymers, e-Polymers, 10 (1), 051, 2010.
  32. Singla, P., Kaur, P., Mehta, R., Berek, D., Upadhyay, S. N., Ring-opening polymerization of lactide using microwave and conventional heating, Procedia Chemistry, 4, 179–185, 2012.
  33. Xu, G., Chen, S., Yan, X., Yang, C., Chen, Z., Synthesis and hydrophilic performance of poly(lactic acid)-poly(ethylene glycol) block copolymers, American Journal of Analytical Chemistry, 7 (3), 299, 2016.
  34. Baimark, Y., Rungseesantivanon, W., Prakymoramas, N., Synthesis of flexible poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) bioplastics by ring-opening polymerization in the presence of chain extender, e-Polymers, 20 (1), 423–429, 2020.
  35. Gadomska-Gajadhur, A., Ruskowski, P., Biocompatible catalysts for lactide polymerization—Catalyst activity, racemization effect, and optimization of the polymerization based on design of experiments, Organic Process Research and Development, 24 (8), 1435–1442, 2020.
  36. Guo, J., Liu, X., Liu, M., Han, M., Liu, Y., Ji, S., Effect of molecular weight of poly(ethylene glycol) on plasticization of poly(L-lactic acid), Polymer, 223, 123720, 2021.
  37. Kricheldorf, H. R., Weidner, S. M., Syntheses of polylactides by means of tin catalysts, Polymer Chemistry, 13, 1618–1647, 2022.
  38. Khattab, M., Abdel Hady, N., Dahman, Y., Green biodegradable polylactide-based polyurethane triblock copolymers reinforced with cellulose nanowhiskers, Journal of Functional Biomaterials, 14 (3), 118, 2023.
  39. Punyodom, W., Limwanich, W., Meepowpan, P., Thapsukhon, B., Ring opening polymerization of ε caprolactone initiated by tin(II) octoate/n hexanol: DSC isoconversional kinetics analysis and polymer synthesis, Designed Monomers and Polymers, 24 (1), 89–97, 2021.
  40. Wang, H. L., Zhang, Y., Tian, M., Zhai, L. F., Wei, Z., Shi, T. J., Preparation and degradability of poly(lactic acid)-poly(ethylene glycol)-poly(lactic acid)/SiO2 hybrid material, Journal of Applied Polymer Science, 110, 3985–3989, 2008.
  41. Rashkov, I., Manolova, N., Li, S. M., Espartero, J. L., Vert, M., Synthesis, characterization, and hydrolytic degradation of PLA/PEO/PLA triblock copolymers with short poly(L-lactic acid) chains, Macromolecules, 29, 50–56, 1996.
  42. Zhang, C., Liao, L., Gong, S., Microwave-assisted synthesis of PLLA–PEG–PLLA triblock copolymers, Macromolecular Rapid Communications, 28 (4), 422–427, 2007.