Skip to main content
SpringerLink
Log in

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

  • Original Paper
  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Abstract

Benzoin (B) end-chain functional macrophotoinitiator of poly(d,l-lactide) homopolymer (B-PDLLA) and poly(ε-caprolactone)-poly(d,l-lactide) (B-PCL-b-PDLLA) diblock copolymer with controlled molecular weights and low polydispersities have been synthesized via ring-opening polymerization (ROP). The ROP of d,l-lactide with benzoin as the initiator and tin octoate (Sn(Oct)2) as the catalyst in bulk at 130 °C formed B-PDLLA polymer. B-PCL-b-PDLLA was synthesized by sequential ROP in two steps. Benzoin (B) end-chain functional macrophotoinitiator of poly(ε-caprolactone) (B-PCL) was first prepared via ROP of ε-caprolactone by using benzoin/Sn(Oct)2 initiating system. The resultant hydroxyl-terminated B-PCL macrophotoinitiator was subsequently utilized as the macroinitiator in the second-step ROP of d,l-lactide to synthesize B-PCL-b-PDLLA. The 1H NMR, FT-IR, GPC, UV, and fluorescence spectroscopic studies revealed that low-polydispersity poly(d,l-lactide) homopolymer and poly(ε-caprolactone)-poly(d,l-lactide) diblock copolymer with benzoin end-groups were obtained. These macrophotoinitiators were used as prepolymers in photoinitiated free radical promoted cationic polymerization for obtaining AB type di- and ABC type tri-block copolymers.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Scheme 3
Fig. 6

Similar content being viewed by others

References

  1. Albertsson AC, Varma IK (2003) Recent developments in ring opening polymerization of lactones for biomedical applications. Biomacromolecules 4:1466–1486

    Article  CAS  Google Scholar 

  2. Lendlein A, Sisson A (2011) Handbook of biodegradable polymers: synthesis, characterization and applications. Wiley, Weinheim

    Book  Google Scholar 

  3. Pilla S (2011) Handbook of bioplastics and biocomposites engineering applications. Wiley, Weinheim

    Book  Google Scholar 

  4. Labet M, Thielemans W (2009) Synthesis of polycaprolactone: a review. Chem Soc Rev 38:3484–3504

    Article  CAS  Google Scholar 

  5. Kricheldorf HR, Kreiser-Saunders I, Stricker A (2000) Polylactones 48. SnOct2-initiated polymerizations of lactide: a mechanistic study. Macromolecules 33:702–709

    Article  CAS  Google Scholar 

  6. Degirmenci M, Hizal G, Yagci Y (2002) Synthesis and characterization of macrophotoinitiators of poly(ε-caprolactone) and their use in block copolymerization. Macromolecules 35:8265–8270

    Article  CAS  Google Scholar 

  7. Martello MT, Schneiderman DK, Hillmyer MA (2014) Synthesis and melt processing of sustainable poly(ε-decalactone)-block-poly(lactide) multiblock thermoplastic elastomers. ACS Sustain Chem Eng 2:2519–2526

    Article  CAS  Google Scholar 

  8. Gardella L, Cavallo D, Colonna S, Fina A, Monticelli O (2014) Novel poly(l-lactide)/Poly(d-lactide)/poly(tetrahydrofuran) multiblock copolymers with a controlled architecture: synthesis and characterization. J Polym Sci Part A Polym Chem 52:3269–3282

    Article  CAS  Google Scholar 

  9. Biela T, Kowalski A, Libiszowski J, Duda A, Penczek S (2006) Progress in polymerization of cyclic esters: mechanisms and synthetic applications. Macromol Symp 240:47–55

    Article  CAS  Google Scholar 

  10. Yagci Y, Jockush S, Turro NJ (2010) Photoinitiated polymerization: advances, challenges, and opportunities. Macromolecules 43:6245–6260

    Article  CAS  Google Scholar 

  11. Corrales T, Catalina F, Peinado C, Allen NS (2003) Free radical macrophotoinitiators:an overview on recent advances. J Photochem Photobiol A Chem 159:103–114

    Article  CAS  Google Scholar 

  12. Fouassier JP, Lalevee J (2012) Photoinitiators for polymer synthesis: scope, reactivity and efficiency. Wiley, KGaA, Weinheim

    Book  Google Scholar 

  13. Yagci Y, Mishra MK (1994) Macroinitiators. In: Mishra MK (ed) Macromolecular design: concept and practice, chap 6. Polymer frontiers international, Inc, New York, pp 229–264

    Google Scholar 

  14. Durmaz YY, Tasdelen MA, Aydogan B, Kahveci MU, Yagci Y (2009) Light induced processes for the synthesis of polymers with complex structures. In: Khosravi E, Yagci Y, Savelyev Y (eds) New smart materials via metal mediated macromolecular engineering, the NATO science for peace and security programme, part 5. Springer, Dordrecht, pp 329–341

    Chapter  Google Scholar 

  15. Degirmenci M, Cianga I, Hizal G, Yagci Y (2002) Synthesis, characterization and application of polymeric photoinitiators prepared by atom transfer radical polymerization and ring-opening polymerization. Polym Preprints 43:22–23

    CAS  Google Scholar 

  16. Yagci Y, Degirmenci M (2003) Advances in controlled/living radical polymerization. In: Matyjaszewski K (ed) ACS symposium series, Chapt. 27, vol 854. American Chemical Society, Washington, DC, pp 383–393

    Google Scholar 

  17. Degirmenci M, Genli N (2009) Synthesis of well-defined telechelic macrophotoinitiator of polystyrene by combination of ATRP and click chemistry. Macromol Chem Phys 210:1617–1623

    Article  CAS  Google Scholar 

  18. Durmaz YY, Yilmaz G, Yagci Y (2007) N-alkoxy pyridinium ion terminated polystyrenes: a facile route to photoinduced block copolymerization. J Poly Sci Part A Poly Chem 45:423–428

    Article  CAS  Google Scholar 

  19. Temel G, Arsu N (2009) One-pot synthesis of water-soluble polymeric photoinitiator via thioxanthonation and sulfonation process. J Photochem Photobiol A Chem 202:63–66

    Article  CAS  Google Scholar 

  20. Degirmenci M, Cianga I, Yagci Y (2002) Synthesis of well-defined polystyrene macrophotoinitiators by atom-transfer radical polymerization. Macromol Chem Phys 203:1279–1284

    Article  CAS  Google Scholar 

  21. Degirmenci M, Alter S, Genli N (2011) Synthesis and characterization of well-defined mid-chain functional macrophotoinitiators of polystyrene by combination of ATRP and ‘‘Click’’ chemistry. Macromol Chem Phys 212:1575–1581

    Article  CAS  Google Scholar 

  22. Degirmenci M (2005) Synthesis and characterization of novel well-defined end-functional macrophotoinitiator of poly(MMA) by ATRP. J Macromol Sci Part A Pure Appl Chem 42:21–30

    Article  Google Scholar 

  23. Degirmenci M (2004) Synthesis of novel well-defined end-functional macrophotoinitiator of poly(e-caprolactone) by ring-opening polymerization. Polym J 36:542–548

    Article  CAS  Google Scholar 

  24. Degirmenci M, Besli PA, Genli N (2014) Synthesis of a well-defined end-chain macrophotoinitiator of poly(ε-caprolactone) by combination of ring-opening polymerization and click chemistry. J Polym Res 21:540–549

    Article  Google Scholar 

  25. Degirmenci M, Gokkkaya C, Durgun M (2016) One-step synthesis of a mid-chain functional macrophotoinitiator of a polystyrene-poly(ε-caprolactone) diblock copolymer via simultaneous ATRP and ROP using a dual-functional photoinitiator. Polym J 48:139–145

    Article  CAS  Google Scholar 

  26. Degirmenci M, Urun T, Durgun M, Barim E (2015) Synthesis of mid-chain functional macrophotoinitiators of poly(d,l-lactide) homopolymer and tetrablock poly(d,l-lactide)-poly(ε-caprolactone) copolymer by ring-opening polymerization. Des Monomers Polym 18(7):669–677

    Article  CAS  Google Scholar 

  27. Save M, Schappacher M, Soum A (2002) Controlled ring-opening polymerization of lactones and lactides initiated by lanthanum isopropoxide, 1. General aspects and kinetic. Macromol Chem Phys 203:889–899

    Article  CAS  Google Scholar 

  28. Bachofner HE, Beringer FM, Meites L (1958) Diaryliodonium salts. V. The electroreduction of diphenyliodonium salts. J Am Chem Soc 80:4269–4274

    Article  CAS  Google Scholar 

  29. Bottcher A, Hasebe K, Hizal G, Yagci Y, Stellberg P, Schnabel W (1991) Initiation of cationic polymerization via oxidation of free radicals using pyridinium salts. Polymer 32:2289–2293

    Article  Google Scholar 

Download references

Acknowledgments

The authors would like to thank Harran University, Scientific Research Council (HÜBAK) for financial support (Project no: 14021).

Author information

Authors and Affiliations

  1. Department of Chemistry, Science Faculty, Harran University, Sanliurfa, 63190, Turkey

    Mustafa Degirmenci, Nalan Benek & Mustafa Durgun

Authors
  1. Mustafa Degirmenci
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Nalan Benek
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mustafa Durgun
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mustafa Degirmenci.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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. 74, 167–181 (2017). https://doi.org/10.1007/s00289-016-1706-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-016-1706-3

Keywords

Search

Navigation