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Novel Well-defined Polystyrene-block-Poly(lactide-co-glycolide) Block Copolymers

Yıl 2023, Cilt: 10 Sayı: 1, 241 - 252, 28.02.2023
https://doi.org/10.18596/jotcsa.1184492

Öz

A facile preparation of polystyrene-block-poly(lactide-co-glycolide) PS-b-PLGA block copolymers was reported in detail. Well-defined PS-b-PLGA block copolymers were successfully obtained via living anionic polymerization and ring-opening polymerization. First, hydroxyl-terminated linear polystyrenes were prepared by living anionic polymerization. The resulting polymers were used as macroinitiators for ring-opening copolymerization of lactide and glycolide in the presence of the 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst in dichloromethane at ambient temperature. Transesterification and formation of DBU-initiated polymers were minimized by optimizing the catalyst concentration. Three block copolymers were synthesized in various molecular weights from 5000 g/mol to 33600 g/mol with low polydispersity. The formation of well-defined PS-b-PLGA block copolymers was followed by nuclear magnetic resonance spectroscopy and size-exclusion chromatography. Thermal properties of the block copolymers were investigated by thermal gravimetric analysis and differential scanning calorimetry. The morphology of the block copolymers was investigated using small-angle X-ray scattering in the bulk and via grazing incidence small-angle X-ray scattering as well as atomic force microscopy in thin film demonstrating organized nanostructures with uniform domain sizes. Overall, this manuscript describes an expanded polymer toolbox for PLGA-based polymers for next-generation lithography applications.

Teşekkür

The author graciously thanks Prof. Marc Hillmyer (UMN), Prof. Frank Bates (UMN), and Dr. Joshua Speros (BASF) for helpful discussion as well as for their financial support. SAXS and GISAXS data were obtained at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory. Parts of this work were carried out in the Characterization Facility, University of Minnesota.

Kaynakça

  • 1. Bates CM, Bates FS. 50th Anniversary Perspective : Block Polymers—Pure Potential. Macromolecules. 2017 Jan 10;50(1):3–22.
  • 2. Lazzari M, López-Quintela MA. Block Copolymers as a Tool for Nanomaterial Fabrication. Adv Mater. 2003 Oct 2;15(19):1583–94.
  • 3. Jackson EA, Hillmyer MA. Nanoporous Membranes Derived from Block Copolymers: From Drug Delivery to Water Filtration. ACS Nano. 2010 Jul 27;4(7):3548–53.
  • 4. Kim HC, Park SM, Hinsberg WD. Block Copolymer Based Nanostructures: Materials, Processes, and Applications to Electronics. Chem Rev. 2010 Jan 13;110(1):146–77.
  • 5. Jung YS, Jung W, Tuller HL, Ross CA. Nanowire Conductive Polymer Gas Sensor Patterned Using Self-Assembled Block Copolymer Lithography. Nano Lett. 2008 Nov 12;8(11):3776–80.
  • 6. Park M, Harrison C, Chaikin P, others. Block Copolymer Lithography: Periodic Arrays of 10. Holes in. 1:1401–4.
  • 7. Bates FS, Hillmyer MA, Lodge TP, Bates CM, Delaney KT, Fredrickson GH. Multiblock Polymers: Panacea or Pandora’s Box? Science. 2012 Apr 27;336(6080):434–40.
  • 8. Darling SB. Directing the self-assembly of block copolymers. Progress in Polymer Science. 2007 Oct;32(10):1152–204.
  • 9. Leibler L. Theory of microphase separation in block copolymers. Macromolecules. 1980;13(6):1602–17.
  • 10. Bates FS. Polymer-Polymer Phase Behavior. Science. 1991 Feb 22;251(4996):898–905.
  • 11. Bates FS, Fredrickson GH. Block copolymers-designer soft materials. Physics today. 2000;52.
  • 12. Luo M, Epps TH. Directed Block Copolymer Thin Film Self-Assembly: Emerging Trends in Nanopattern Fabrication. Macromolecules. 2013 Oct 8;46(19):7567–79.
  • 13. Klumperman B. Reversible Deactivation Radical Polymerization. In: John Wiley & Sons, Inc., editor. Encyclopedia of Polymer Science and Technology [Internet]. 1st ed. Wiley; 2015 [cited 2023 Feb 8]. p. 1–27.
  • 14. Matyjaszewski K. Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives. Macromolecules. 2012 May 22;45(10):4015–39.
  • 15. Ouchi M, Sawamoto M. 50th Anniversary Perspective : Metal-Catalyzed Living Radical Polymerization: Discovery and Perspective. Macromolecules. 2017 Apr 11;50(7):2603–14.
  • 16. Perrier S. 50th Anniversary Perspective : RAFT Polymerization—A User Guide. Macromolecules. 2017 Oct 10;50(19):7433–47.
  • 17. Moad G. RAFT polymerization to form stimuli-responsive polymers. Polym Chem. 2017;8(1):177–219.
  • 18. Nicolas J, Guillaneuf Y, Lefay C, Bertin D, Gigmes D, Charleux B. Nitroxide-mediated polymerization. Progress in Polymer Science. 2013 Jan;38(1):63–235.
  • 19. Vanderlaan ME, Hillmyer MA. “Uncontrolled” Preparation of Disperse Poly(lactide)- block -poly(styrene)- block -poly(lactide) for Nanopatterning Applications. Macromolecules. 2016 Nov 8;49(21):8031–40.
  • 20. Szwarc M. ‘Living’polymers. Nature. 1956;178:1168–9.
  • 21. Hirao A, Loykulnant S, Ishizone T. Recent advance in living anionic polymerization of functionalized styrene derivatives. Progress in Polymer Science. 2002 Oct;27(8):1399–471.
  • 22. Hadjichristidis N, Pitsikalis M, Pispas S, Iatrou H. Polymers with Complex Architecture by Living Anionic Polymerization. Chem Rev. 2001 Dec 1;101(12):3747–92.
  • 23. Dechy-Cabaret O, Martin-Vaca B, Bourissou D. Controlled Ring-Opening Polymerization of Lactide and Glycolide. Chem Rev. 2004 Dec 1;104(12):6147–76.
  • 24. Meduri A, Fuoco T, Lamberti M, Pellecchia C, Pappalardo D. Versatile Copolymerization of Glycolide and rac -Lactide by Dimethyl(salicylaldiminato)aluminum Compounds. Macromolecules. 2014 Jan 28;47(2):534–43.
  • 25. Albertsson AC, Varma IK. Recent Developments in Ring Opening Polymerization of Lactones for Biomedical Applications. Biomacromolecules. 2003 Nov 1;4(6):1466–86.
  • 26. Chiellini E, Solaro R. Biodegradable Polymeric Materials. Adv Mater. 1996 Apr;8(4):305–13.
  • 27. Saba SA, Mousavi MPS, Bühlmann P, Hillmyer MA. Hierarchically Porous Polymer Monoliths by Combining Controlled Macro- and Microphase Separation. J Am Chem Soc. 2015 Jul 22;137(28):8896–9.
  • 28. Altay E, Jang YJ, Kua XQ, Hillmyer MA. Synthesis, Microstructure, and Properties of High-Molar-Mass Polyglycolide Copolymers with Isolated Methyl Defects. Biomacromolecules. 2021 Jun 14;22(6):2532–43.
  • 29. Kemo VM, Schmidt C, Zhang Y, Beuermann S. Low Temperature Ring-Opening Polymerization of Diglycolide Using Organocatalysts with PEG as Macroinitiator. Macromol Chem Phys. 2016 Apr;217(7):842–9.
  • 30. Qian H, Wohl AR, Crow JT, Macosko CW, Hoye TR. A Strategy for Control of “Random” Copolymerization of Lactide and Glycolide: Application to Synthesis of PEG- b -PLGA Block Polymers Having Narrow Dispersity. Macromolecules. 2011 Sep 27;44(18):7132–40.
  • 31. Wilts EM, Gula A, Davis C, Chartrain N, Williams CB, Long TE. Vat photopolymerization of liquid, biodegradable PLGA-based oligomers as tissue scaffolds. European Polymer Journal. 2020 May;130:109693.
  • 32. Zalusky AS, Olayo-Valles R, Wolf JH, Hillmyer MA. Ordered Nanoporous Polymers from Polystyrene−Polylactide Block Copolymers. J Am Chem Soc. 2002 Oct 1;124(43):12761–73.
  • 33. Brown HA, De Crisci AG, Hedrick JL, Waymouth RM. Amidine-Mediated Zwitterionic Polymerization of Lactide. ACS Macro Lett. 2012 Sep 18;1(9):1113–5.
  • 34. Chu CC. Differential scanning calorimetric study of the crystallization kinetics of polyglycolic acid at high undercooling. Polymer. 1980 Dec;21(12):1480–2.
  • 35. Wang D, Russell TP. Advances in Atomic Force Microscopy for Probing Polymer Structure and Properties. Macromolecules. 2018 Jan 9;51(1):3–24.
  • 36. Yao L, Oquendo LE, Schulze MW, Lewis RM, Gladfelter WL, Hillmyer MA. Poly(cyclohexylethylene)- block -Poly(lactide) Oligomers for Ultrasmall Nanopatterning Using Atomic Layer Deposition. ACS Appl Mater Interfaces. 2016 Mar 23;8(11):7431–9.
  • 37. Posselt D, Zhang J, Smilgies DM, Berezkin AV, Potemkin II, Papadakis CM. Restructuring in block copolymer thin films: In situ GISAXS investigations during solvent vapor annealing. Progress in Polymer Science. 2017 Mar;66:80–115.
  • 38. Vora A, Wojtecki RJ, Schmidt K, Chunder A, Cheng JY, Nelson A, et al. Development of polycarbonate-containing block copolymers for thin film self-assembly applications. Polym Chem. 2016;7(4):940–50.
Yıl 2023, Cilt: 10 Sayı: 1, 241 - 252, 28.02.2023
https://doi.org/10.18596/jotcsa.1184492

Öz

Kaynakça

  • 1. Bates CM, Bates FS. 50th Anniversary Perspective : Block Polymers—Pure Potential. Macromolecules. 2017 Jan 10;50(1):3–22.
  • 2. Lazzari M, López-Quintela MA. Block Copolymers as a Tool for Nanomaterial Fabrication. Adv Mater. 2003 Oct 2;15(19):1583–94.
  • 3. Jackson EA, Hillmyer MA. Nanoporous Membranes Derived from Block Copolymers: From Drug Delivery to Water Filtration. ACS Nano. 2010 Jul 27;4(7):3548–53.
  • 4. Kim HC, Park SM, Hinsberg WD. Block Copolymer Based Nanostructures: Materials, Processes, and Applications to Electronics. Chem Rev. 2010 Jan 13;110(1):146–77.
  • 5. Jung YS, Jung W, Tuller HL, Ross CA. Nanowire Conductive Polymer Gas Sensor Patterned Using Self-Assembled Block Copolymer Lithography. Nano Lett. 2008 Nov 12;8(11):3776–80.
  • 6. Park M, Harrison C, Chaikin P, others. Block Copolymer Lithography: Periodic Arrays of 10. Holes in. 1:1401–4.
  • 7. Bates FS, Hillmyer MA, Lodge TP, Bates CM, Delaney KT, Fredrickson GH. Multiblock Polymers: Panacea or Pandora’s Box? Science. 2012 Apr 27;336(6080):434–40.
  • 8. Darling SB. Directing the self-assembly of block copolymers. Progress in Polymer Science. 2007 Oct;32(10):1152–204.
  • 9. Leibler L. Theory of microphase separation in block copolymers. Macromolecules. 1980;13(6):1602–17.
  • 10. Bates FS. Polymer-Polymer Phase Behavior. Science. 1991 Feb 22;251(4996):898–905.
  • 11. Bates FS, Fredrickson GH. Block copolymers-designer soft materials. Physics today. 2000;52.
  • 12. Luo M, Epps TH. Directed Block Copolymer Thin Film Self-Assembly: Emerging Trends in Nanopattern Fabrication. Macromolecules. 2013 Oct 8;46(19):7567–79.
  • 13. Klumperman B. Reversible Deactivation Radical Polymerization. In: John Wiley & Sons, Inc., editor. Encyclopedia of Polymer Science and Technology [Internet]. 1st ed. Wiley; 2015 [cited 2023 Feb 8]. p. 1–27.
  • 14. Matyjaszewski K. Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives. Macromolecules. 2012 May 22;45(10):4015–39.
  • 15. Ouchi M, Sawamoto M. 50th Anniversary Perspective : Metal-Catalyzed Living Radical Polymerization: Discovery and Perspective. Macromolecules. 2017 Apr 11;50(7):2603–14.
  • 16. Perrier S. 50th Anniversary Perspective : RAFT Polymerization—A User Guide. Macromolecules. 2017 Oct 10;50(19):7433–47.
  • 17. Moad G. RAFT polymerization to form stimuli-responsive polymers. Polym Chem. 2017;8(1):177–219.
  • 18. Nicolas J, Guillaneuf Y, Lefay C, Bertin D, Gigmes D, Charleux B. Nitroxide-mediated polymerization. Progress in Polymer Science. 2013 Jan;38(1):63–235.
  • 19. Vanderlaan ME, Hillmyer MA. “Uncontrolled” Preparation of Disperse Poly(lactide)- block -poly(styrene)- block -poly(lactide) for Nanopatterning Applications. Macromolecules. 2016 Nov 8;49(21):8031–40.
  • 20. Szwarc M. ‘Living’polymers. Nature. 1956;178:1168–9.
  • 21. Hirao A, Loykulnant S, Ishizone T. Recent advance in living anionic polymerization of functionalized styrene derivatives. Progress in Polymer Science. 2002 Oct;27(8):1399–471.
  • 22. Hadjichristidis N, Pitsikalis M, Pispas S, Iatrou H. Polymers with Complex Architecture by Living Anionic Polymerization. Chem Rev. 2001 Dec 1;101(12):3747–92.
  • 23. Dechy-Cabaret O, Martin-Vaca B, Bourissou D. Controlled Ring-Opening Polymerization of Lactide and Glycolide. Chem Rev. 2004 Dec 1;104(12):6147–76.
  • 24. Meduri A, Fuoco T, Lamberti M, Pellecchia C, Pappalardo D. Versatile Copolymerization of Glycolide and rac -Lactide by Dimethyl(salicylaldiminato)aluminum Compounds. Macromolecules. 2014 Jan 28;47(2):534–43.
  • 25. Albertsson AC, Varma IK. Recent Developments in Ring Opening Polymerization of Lactones for Biomedical Applications. Biomacromolecules. 2003 Nov 1;4(6):1466–86.
  • 26. Chiellini E, Solaro R. Biodegradable Polymeric Materials. Adv Mater. 1996 Apr;8(4):305–13.
  • 27. Saba SA, Mousavi MPS, Bühlmann P, Hillmyer MA. Hierarchically Porous Polymer Monoliths by Combining Controlled Macro- and Microphase Separation. J Am Chem Soc. 2015 Jul 22;137(28):8896–9.
  • 28. Altay E, Jang YJ, Kua XQ, Hillmyer MA. Synthesis, Microstructure, and Properties of High-Molar-Mass Polyglycolide Copolymers with Isolated Methyl Defects. Biomacromolecules. 2021 Jun 14;22(6):2532–43.
  • 29. Kemo VM, Schmidt C, Zhang Y, Beuermann S. Low Temperature Ring-Opening Polymerization of Diglycolide Using Organocatalysts with PEG as Macroinitiator. Macromol Chem Phys. 2016 Apr;217(7):842–9.
  • 30. Qian H, Wohl AR, Crow JT, Macosko CW, Hoye TR. A Strategy for Control of “Random” Copolymerization of Lactide and Glycolide: Application to Synthesis of PEG- b -PLGA Block Polymers Having Narrow Dispersity. Macromolecules. 2011 Sep 27;44(18):7132–40.
  • 31. Wilts EM, Gula A, Davis C, Chartrain N, Williams CB, Long TE. Vat photopolymerization of liquid, biodegradable PLGA-based oligomers as tissue scaffolds. European Polymer Journal. 2020 May;130:109693.
  • 32. Zalusky AS, Olayo-Valles R, Wolf JH, Hillmyer MA. Ordered Nanoporous Polymers from Polystyrene−Polylactide Block Copolymers. J Am Chem Soc. 2002 Oct 1;124(43):12761–73.
  • 33. Brown HA, De Crisci AG, Hedrick JL, Waymouth RM. Amidine-Mediated Zwitterionic Polymerization of Lactide. ACS Macro Lett. 2012 Sep 18;1(9):1113–5.
  • 34. Chu CC. Differential scanning calorimetric study of the crystallization kinetics of polyglycolic acid at high undercooling. Polymer. 1980 Dec;21(12):1480–2.
  • 35. Wang D, Russell TP. Advances in Atomic Force Microscopy for Probing Polymer Structure and Properties. Macromolecules. 2018 Jan 9;51(1):3–24.
  • 36. Yao L, Oquendo LE, Schulze MW, Lewis RM, Gladfelter WL, Hillmyer MA. Poly(cyclohexylethylene)- block -Poly(lactide) Oligomers for Ultrasmall Nanopatterning Using Atomic Layer Deposition. ACS Appl Mater Interfaces. 2016 Mar 23;8(11):7431–9.
  • 37. Posselt D, Zhang J, Smilgies DM, Berezkin AV, Potemkin II, Papadakis CM. Restructuring in block copolymer thin films: In situ GISAXS investigations during solvent vapor annealing. Progress in Polymer Science. 2017 Mar;66:80–115.
  • 38. Vora A, Wojtecki RJ, Schmidt K, Chunder A, Cheng JY, Nelson A, et al. Development of polycarbonate-containing block copolymers for thin film self-assembly applications. Polym Chem. 2016;7(4):940–50.
Toplam 38 adet kaynakça vardır.

Ayrıntılar

Birincil Dil İngilizce
Konular Polimer Bilimi ve Teknolojileri
Bölüm Makaleler
Yazarlar

Ozcan Altintas 0000-0003-3725-4613

Yayımlanma Tarihi 28 Şubat 2023
Gönderilme Tarihi 12 Ekim 2022
Kabul Tarihi 9 Ocak 2023
Yayımlandığı Sayı Yıl 2023 Cilt: 10 Sayı: 1

Kaynak Göster

Vancouver Altintas O. Novel Well-defined Polystyrene-block-Poly(lactide-co-glycolide) Block Copolymers. JOTCSA. 2023;10(1):241-52.