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Synthesis of an (AB)4-type Star Block Copolymer of L-lactide and Cyclohexene Oxide from a Tetra-Arm Telechelic Macrophotoinitiator

Year 2018, Volume: 5 Issue: 3, 1105 - 1118, 01.09.2018
https://doi.org/10.18596/jotcsa.450986

Abstract

A
multi-step reaction process was applied for the synthesis of a novel and
well-defined star-shaped telechelic macrophotoinitiator with four
poly(L-lactide) (PLLA) arms bearing photoinitiating benzoin groups at the chain
ends (PLLA-PI)4. To achieve this,
2,2-bis(hydroxymethyl)-1,3-propanediol was used as the initiator which
constitutes the core of the star-shaped polymeric scaffold. Benzoin
photoreactive end groups of the telechelic (PLLA-PI)4, capable of
entering into further polymerization, allowed its use as a prepolymer in
photoinduced free radical promoted cationic polymerization with cyclohexene
oxide (CHO) monomer at
l=350 nm to produce an (AB)4-type
star-shaped block copolymer composed of both esteric L-lactide and etheric
cyclohexene oxide chains on each arm, (PLLA-PCHO)4.
Structural analysis and characterization of all intermediate and final
compounds were done by a series of analytical and spectral methods. Molecular
weights of the prepared polymers up to telechelic macrophotoinitiator (PLLA-PI)4
were determined based on 1H-NMR (Mn
H-NMR
), GPC (Mn exp)
analyses and theoretical calculations (Mn
theo
) and were found to be in good agreement with each other. The thermal
behaviors of the polymers synthesized were investigated by thermogravimetric
and differential thermal analysis (TG/DTA). The melting temperature for
(PLLA-PCHO)4 was found higher compared to the other homo-type
polymers in the literature. The thermogravimetric (TG) analyses showed that
introduction of the thermally stable PCHO segment into the structure via
photopolymerization increased its stability shifting its decomposition
temperature to the higher values compared to the prepolymers.

References

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  • 2. Tasdelen MA, Kahveci MU, Yagci Y. Telechelic polymers by living and controlled/living polymerization methods. Prog Polym Sci. 2011;36(4):455-567.
  • 3. Yagci Y, Onen A, Schnabel W. Block copolymers by combination of radical and promoted cationic polymerization routes. Macromolecules. 1991;24(16):4620-3.
  • 4. Kennedy JP, Iván B. Designed Polymers by Carbocationic Macromolecular Engineering: Theory and Practice. Munich - New York: Hanser-Gardner Publications; 1992. 167 p.
  • 5. Fontanille M. 27 - Carbanionic Polymerization: Termination and Functionalization. In: Bevington JC, Allen G, editors. Comprehensive Polymer Science and Supplements. 3. Amsterdam: Pergamon; 1989. p. 425-32.
  • 6. Yagci Y, Nuyken O, Graubner V-M. Telechelic Polymers. In: Kroschwitz JI, editor. Encyclopedia of Polymer Science and Technology. 12. 3rd ed. New York: John Wiley & Sons, Inc.; 2005. p. 57-130.
  • 7. Mannion AM, Bates FS, Macosko CW. Synthesis and rheology of branched multiblock polymers based on polylactide. Macromolecules. 2016;49(12):4587-98.
  • 8. Guillaume SM. Recent advances in ring-opening polymerization strategies toward α, ω-hydroxy telechelic polyesters and resulting copolymers. Eur Polym J. 2013;49(4):768-79.
  • 9. Degirmenci M, Genli N. Synthesis of Well‐Defined Telechelic Macrophotoinitiator of Polystyrene by Combination of ATRP and Click Chemistry. Macromol Chem Phys. 2009;210(19):1617-23.
  • 10. Akeroyd N, Klumperman B. The combination of living radical polymerization and click chemistry for the synthesis of advanced macromolecular architectures. Eur Polym J. 2011;47(6):1207-31.
  • 11. Sumerlin BS, Vogt AP. Macromolecular engineering through click chemistry and other efficient transformations. Macromolecules. 2009;43(1):1-13.
  • 12. Wang CW, Liu C, Zhu XW, Yang ZY, Sun HF, Kong DL, et al. Synthesis of well‐defined star‐shaped poly (ε‐caprolactone)/poly (ethylbene glycol) amphiphilic conetworks by combination of ring opening polymerization and “click” chemistry. J Polym Sci, Part A: Polym Chem. 2016;54(3):407-17.
  • 13. Sivaram S, Chowdhury SR. Synthesis of Functional Polymers of Polar and Nonpolar Monomers by Living and/or Controlled Polymerization. Functional Polymers: Apple Academic Press; 2017. p. 29-82.
  • 14. Yagci Y, Tasdelen MA. Mechanistic transformations involving living and controlled/living polymerization methods. Prog Polym Sci. 2006;31(12):1133-70.
  • 15. Jakubowski W, Matyjaszewski K. New Segmented Copolymers by Combination of Atom Transfer Radical Polymerization and Ring Opening Polymerization. Macromol Symp. 2006;240:213-23.
  • 16. Yagci Y, Jockusch S, Turro NJ. Photoinitiated polymerization: advances, challenges, and opportunities. Macromolecules. 2010;43(15):6245-60.
  • 17. Wen Y, Jiang X, Liu R, Yin J. Amphipathic hyperbranched polymeric thioxanthone photoinitiators (AHPTXs): Synthesis, characterization and photoinitiated polymerization. Polymer. 2009;50(16):3917-23.
  • 18. Corrales T, Catalina F, Peinado C, Allen N. Free radical macrophotoinitiators: an overview on recent advances. J Photochem Photobiol A: Chem. 2003;159(2):103-14.
  • 19. Yagci Y, Mishra MK. Macroinitiators for Chain Polymerization. In: Mishra M, editor. Macromolecular Design : Concept and Practice. New York: Polymer Frontiers International Inc.; 1994. p. 229-64.
  • 20. Durmaz YY, Tasdelen MA, Aydogan B, Kahveci MU, Yagci Y. Light induced processes for the synthesis of polymers with complex structures. New smart materials via metal mediated macromolecular engineering: Springer; 2009. p. 329-41.
  • 21. Degirmenci M, Benek N, Durgun M. Synthesis of benzoin end-chain functional macrophotoinitiator of poly (D, L-lactide) homopolymer and poly (ε-caprolactone)-poly (D, L-lactide) diblock copolymer by ROP and their use in photoinduced free radical promoted cationic copolymerization. Polym Bull. 2017;74(1):167-81.
  • 22. Degirmenci M, Besli PA, Genli N. Synthesis of a well-defined end-chain macrophotoinitiator of poly (ε−caprolactone) by combination of ring-opening polymerization and click chemistry. J Polym Res. 2014;21(9):540.
  • 23. Uyar Z, Degirmenci M, Genli N, Yilmaz A. Synthesis of well-defined bisbenzoin end-functionalized poly (ε-caprolactone) macrophotoinitiator by combination of ROP and click chemistry and its use in the synthesis of star copolymers by photoinduced free radical promoted cationic polymerization. Designed Monomers and Polymers. 2017;20(1):42-53.
  • 24. Uyar Z, Durgun M, Yavuz MS, Abaci MB, Arslan U, Degirmenci M. Two-arm PCL and PLLA macrophotoinitiators with benzoin end-functional groups by combination of ROP and click chemistry and their use in the synthesis of A2B2 type miktoarm star copolymers. Polymer. 2017;123:153-68.
  • 25. Yagci Y, Degirmenci M. Photoinduced Free Radical Promoted Cationic Block Copolymerization by Using Macrophotoinitiators Prepared by ATRP and Ring-Opening Polymerization Methods. Advances in Controlled/Living Radical Polymerization. ACS Symposium Series. 854: American Chemical Society; 2003. p. 383-93.
  • 26. Yaḡci Y, Kornowski A, Schnabel W. N‐alkoxy‐pyridinium and N‐alkoxy‐quinolinium salts as initiators for cationic photopolymerizations. J Polym Sci, Part A: Polym Chem. 1992;30(9):1987-91.
  • 27. Save M, Schappacher M, Soum A. Controlled Ring‐Opening Polymerization of Lactones and Lactides Initiated by Lanthanum Isopropoxide, 1. General Aspects and Kinetics. Macromol Chem Phys. 2002;203(5‐6):889-99.
Year 2018, Volume: 5 Issue: 3, 1105 - 1118, 01.09.2018
https://doi.org/10.18596/jotcsa.450986

Abstract

References

  • 1. Verso FL, Likos CN. End-functionalized polymers: Versatile building blocks for soft materials. Polymer. 2008;49(6):1425-34.
  • 2. Tasdelen MA, Kahveci MU, Yagci Y. Telechelic polymers by living and controlled/living polymerization methods. Prog Polym Sci. 2011;36(4):455-567.
  • 3. Yagci Y, Onen A, Schnabel W. Block copolymers by combination of radical and promoted cationic polymerization routes. Macromolecules. 1991;24(16):4620-3.
  • 4. Kennedy JP, Iván B. Designed Polymers by Carbocationic Macromolecular Engineering: Theory and Practice. Munich - New York: Hanser-Gardner Publications; 1992. 167 p.
  • 5. Fontanille M. 27 - Carbanionic Polymerization: Termination and Functionalization. In: Bevington JC, Allen G, editors. Comprehensive Polymer Science and Supplements. 3. Amsterdam: Pergamon; 1989. p. 425-32.
  • 6. Yagci Y, Nuyken O, Graubner V-M. Telechelic Polymers. In: Kroschwitz JI, editor. Encyclopedia of Polymer Science and Technology. 12. 3rd ed. New York: John Wiley & Sons, Inc.; 2005. p. 57-130.
  • 7. Mannion AM, Bates FS, Macosko CW. Synthesis and rheology of branched multiblock polymers based on polylactide. Macromolecules. 2016;49(12):4587-98.
  • 8. Guillaume SM. Recent advances in ring-opening polymerization strategies toward α, ω-hydroxy telechelic polyesters and resulting copolymers. Eur Polym J. 2013;49(4):768-79.
  • 9. Degirmenci M, Genli N. Synthesis of Well‐Defined Telechelic Macrophotoinitiator of Polystyrene by Combination of ATRP and Click Chemistry. Macromol Chem Phys. 2009;210(19):1617-23.
  • 10. Akeroyd N, Klumperman B. The combination of living radical polymerization and click chemistry for the synthesis of advanced macromolecular architectures. Eur Polym J. 2011;47(6):1207-31.
  • 11. Sumerlin BS, Vogt AP. Macromolecular engineering through click chemistry and other efficient transformations. Macromolecules. 2009;43(1):1-13.
  • 12. Wang CW, Liu C, Zhu XW, Yang ZY, Sun HF, Kong DL, et al. Synthesis of well‐defined star‐shaped poly (ε‐caprolactone)/poly (ethylbene glycol) amphiphilic conetworks by combination of ring opening polymerization and “click” chemistry. J Polym Sci, Part A: Polym Chem. 2016;54(3):407-17.
  • 13. Sivaram S, Chowdhury SR. Synthesis of Functional Polymers of Polar and Nonpolar Monomers by Living and/or Controlled Polymerization. Functional Polymers: Apple Academic Press; 2017. p. 29-82.
  • 14. Yagci Y, Tasdelen MA. Mechanistic transformations involving living and controlled/living polymerization methods. Prog Polym Sci. 2006;31(12):1133-70.
  • 15. Jakubowski W, Matyjaszewski K. New Segmented Copolymers by Combination of Atom Transfer Radical Polymerization and Ring Opening Polymerization. Macromol Symp. 2006;240:213-23.
  • 16. Yagci Y, Jockusch S, Turro NJ. Photoinitiated polymerization: advances, challenges, and opportunities. Macromolecules. 2010;43(15):6245-60.
  • 17. Wen Y, Jiang X, Liu R, Yin J. Amphipathic hyperbranched polymeric thioxanthone photoinitiators (AHPTXs): Synthesis, characterization and photoinitiated polymerization. Polymer. 2009;50(16):3917-23.
  • 18. Corrales T, Catalina F, Peinado C, Allen N. Free radical macrophotoinitiators: an overview on recent advances. J Photochem Photobiol A: Chem. 2003;159(2):103-14.
  • 19. Yagci Y, Mishra MK. Macroinitiators for Chain Polymerization. In: Mishra M, editor. Macromolecular Design : Concept and Practice. New York: Polymer Frontiers International Inc.; 1994. p. 229-64.
  • 20. Durmaz YY, Tasdelen MA, Aydogan B, Kahveci MU, Yagci Y. Light induced processes for the synthesis of polymers with complex structures. New smart materials via metal mediated macromolecular engineering: Springer; 2009. p. 329-41.
  • 21. Degirmenci M, Benek N, Durgun M. Synthesis of benzoin end-chain functional macrophotoinitiator of poly (D, L-lactide) homopolymer and poly (ε-caprolactone)-poly (D, L-lactide) diblock copolymer by ROP and their use in photoinduced free radical promoted cationic copolymerization. Polym Bull. 2017;74(1):167-81.
  • 22. Degirmenci M, Besli PA, Genli N. Synthesis of a well-defined end-chain macrophotoinitiator of poly (ε−caprolactone) by combination of ring-opening polymerization and click chemistry. J Polym Res. 2014;21(9):540.
  • 23. Uyar Z, Degirmenci M, Genli N, Yilmaz A. Synthesis of well-defined bisbenzoin end-functionalized poly (ε-caprolactone) macrophotoinitiator by combination of ROP and click chemistry and its use in the synthesis of star copolymers by photoinduced free radical promoted cationic polymerization. Designed Monomers and Polymers. 2017;20(1):42-53.
  • 24. Uyar Z, Durgun M, Yavuz MS, Abaci MB, Arslan U, Degirmenci M. Two-arm PCL and PLLA macrophotoinitiators with benzoin end-functional groups by combination of ROP and click chemistry and their use in the synthesis of A2B2 type miktoarm star copolymers. Polymer. 2017;123:153-68.
  • 25. Yagci Y, Degirmenci M. Photoinduced Free Radical Promoted Cationic Block Copolymerization by Using Macrophotoinitiators Prepared by ATRP and Ring-Opening Polymerization Methods. Advances in Controlled/Living Radical Polymerization. ACS Symposium Series. 854: American Chemical Society; 2003. p. 383-93.
  • 26. Yaḡci Y, Kornowski A, Schnabel W. N‐alkoxy‐pyridinium and N‐alkoxy‐quinolinium salts as initiators for cationic photopolymerizations. J Polym Sci, Part A: Polym Chem. 1992;30(9):1987-91.
  • 27. Save M, Schappacher M, Soum A. Controlled Ring‐Opening Polymerization of Lactones and Lactides Initiated by Lanthanum Isopropoxide, 1. General Aspects and Kinetics. Macromol Chem Phys. 2002;203(5‐6):889-99.
There are 27 citations in total.

Details

Primary Language English
Subjects Chemical Engineering
Journal Section Articles
Authors

Zafer Uyar

Emel Kaya This is me 0000-0002-4714-7152

Publication Date September 1, 2018
Submission Date August 4, 2018
Acceptance Date September 22, 2018
Published in Issue Year 2018 Volume: 5 Issue: 3

Cite

Vancouver Uyar Z, Kaya E. Synthesis of an (AB)4-type Star Block Copolymer of L-lactide and Cyclohexene Oxide from a Tetra-Arm Telechelic Macrophotoinitiator. JOTCSA. 2018;5(3):1105-18.