One-Pot Synthesis of Block Copolymers via ATRP and ROP Using PCL Macroinitiator

Öz

Poly(lactide)-b-poly(ε-caprolactone)-b-poly(styrene) triblock copolymers were synthesized simultaneously by one-pot method using atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP) in one step. Firstly, brominated poly(ε-caprolactone) (PCL-Br) as macroinitiator was made via ROP of ε-caprolactone (ε-CL) in the existence of tin(II) 2-ethyl hexanoate at 110 °C followed by esterification with 2-bromopropionyl bromide. With the one-pot method, the simultaneously via ROP of D, Llactide in the existence of tin(II) 2-ethyl hexanoate and ATRP of styrene (St) monomer with PCL-Br macroinitiator in the presence of CuCl/PMDETA system using [I]: [CuCl]:[PMDETA]=1:1:3 molar ratios at 120 °C in toluene was performed. Thus, the block copolymers with controlled molecular weights and moderately narrow polydispersities were obtained. Principal parameters, such as monomer concentration, initiator concentration, and polymerization time, which effect the one-pot polymerization were investigated. The polymers obtained were characterized using 1H NMR, FTIR, and GPC technique.

Anahtar Kelimeler

• styrene
• atom transfer radical polymerization
• ring-opening polymerization
• D
• L-lactide
• e-caprolactone

PCL Makro Başlatıcı Kullanarak ATRP ve ROP ile Blok Kopolimerlerin Tek Basamakta Sentezi

Öz

Poli(laktid)-b-poli(ε-kaprolakton)-b-poli(stiren) üç bloklu kopolimerler atom transfer radikal polimerizasyonu ve halka açılma polimerizasyonuyla aynı anda bir basamakta tek kap yöntemiyle sentezlendi. İlk olarak, ε-kaprolakton'nun (ε-CL) kalay (II) 2-etilheksanoat katalizörü varlığında 110 °C'de halka açılma polimerizasyonuyla PCL sentezlenip, ardından 2-bromopropiyonil bromür ile esterleşmesi sonucu bromlanmış poli(ε-kaprolakton) (PCL-Br) makro başlatıcı olarak hazırlanmıştır. Tek kap yöntemiyle, stiren (St) monomerinin PCL-Br makro başlatıcısıyla CuCl/PMDETA sistemi varlığında [I]:[CuCl]:[PMDETA]=1:1:3 mol oranları kullanılarak, 120 °C’de toluen içinde ATRP'si ile ve D, L laktidin HAP'nu aynı anda gerçekleşti. Böylece, kontrollü molekül ağırlıklarına ve orta derecede dar polidispersitelere sahip blok kopolimerler elde edildi. Tek kap polimerizasyonunu etkileyen monomer konsantrasyonu, başlatıcı konsantrasyonu ve polimerizasyon süresi gibi temel parametreler araştırıldı. Elde edilen polimerler, 1H NMR, FTIR ve GPC teknikleri kullanılarak karakterize edildi.

Anahtar Kelimeler

• stiren
• atom transfer radikal polimerizasyonu
• halka açılma polimerizasyonu
• D
• L-laktid
• e-kaprolakton

Kaynakça

1. Allı S, Allı A, Hazer B, 2012. Hyperbranched homo and thermoresponsive graft copolymers by using ATRP-macromonomer initiators. Journal of Applied Polymer Science, 124(1):536–548.
2. Allı A, Allı S, Becer CR, Hazer B, 2016. Nitroxide-mediated copolymerization of styrene and pentafluorostyrene initiated by polymeric linoleic acid. European Journal of Lipid Science and Technology, 118(2):279–287.
3. Allı A, Allı S, Becer CR, Hazer B, 2014. One-pot synthesis of poly(linoleic acid)-g-poly(styrene)-g-poly(ε- caprolactone) graft copolymers. Journal of the American Oil Chemists’ Society, 91(5):849–858.
4. Aydogan C, Kutahya C, Allushi A, Yilmaz G, Yagci Y, 2017. Block copolymer synthesis in one shot concurrent metal-free ATRP and ROP processes under sunlight. Polymer Chemistry, 8(19):2899–2903.
5. Benoit L, Maric M, 2008. Nitroxide-Mediated Synthesis of Poly (poly(ethylene glycol) acrylate) (PPEGA) Comb-Like Homopolymers and Block Copolymers. Macromolecules, 41:7870–7880.
6. Breitenbach A, Pistel KF, Kissel T, 2000. Biodegradable comb polyesters. Part II. Erosion and release properties of poly(vinyl alcohol)-g-poly(lactic-co-glycolic acid). Polymer, 41(13):4781–4792.
7. Broström J, Boss A, Chronakis IS, 2004. Biodegradable films of partly branched poly(L-lactide)-co-poly(ε-caprolactone) copolymer: Modulation of phase morphology, plasticization properties and thermal depolymerization. Biomacromolecules, 5(3):1124–1134.
8. Choochottiros C, Park E, Chin IJ, 2012. Synthesis and characterization of polylactide-poly(methyl methacrylate) copolymer by combining of ROP and AGET ATRP. Journal of Industrial and Engineering Chemistry, 18(3):993–1000.

9. Cordova A, Hult A, Hult K, Ihre H, Iversen T, Malmstrom E, 1998. Synthesis of a poly(ε-caprolactone) monosubstituted first generation dendrimer by lipase catalysis. Journal of the American Chemical Society, 120(51):13521–13522.
10. Davis K A, Matyjaszewski K, 2001. ABC triblock copolymers prepared using atom transfer radical polymerization techniques. Macromolecules 34(7):2101–2107.
11. Deng G, Ma D, Xu Z, 2007. Synthesis of ABC-type miktoarm star polymers by “click” chemistry, ATRP and ROP. European Polymer Journal, 43(4):1179–1187.
12. Finne A, Albertsson AC, 2002. Controlled synthesis of star-shaped L-lactide polymers using new spirocyclic tin initiators. Biomacromolecules, 3(4):684–690.
13. Haddleton DM, Waterson C, Derrick PJ, Jasieczek CB, Shooter AJ, 1997. Monohydroxy terminally functionalised poly (methyl methacrylate) from atom transfer radical polymerisation catalyst and hydroxy functional alkyl bromide initiator leads to a-hydroxy functional PMMA with controlled Mn and PDI. Control, 4(c):683–684.
14. Hasanoğlu ÖE, Sarı N, 2020. Use of immobilized novel dendritic molecules as a marker for the detection of glucose in artificial urine. Journal of Molecular Structure, 1201:127134.
15. Hasanoğlu ÖE, Yetim NK, Nartop D, Sarı N, 2021. Ensuring traceability of organophosphate pesticides (OPs) through enzyme immobilized spheres. Journal of the Iranian Chemical Society, 18:1749–1759.
16. Hawker CJ, Bosman AW, Harth E, 2001. New polymer synthesis by nitroxide mediated living radical polymerizations. Chemical Reviews, 101(12):3661–3688.
17. He X, Liang L, Xie M, Zhang Y, Lin S, Yan D, 2007. Synthesis of novel linear PEO-b-PS-b-PCL triblock copolymers by the combination of ATRP, ROP, and a click reaction. Macromolecular Chemistry and Physics, 208(16):1797–1802.
18. Huang CF, Chen WH, Aimi J, Huang YS, Venkatesan S, Chiang YW, Huang SH, Kuo SW, Chen, T, 2018. Synthesis of well-defined PCL-b-PnBA-b-PMMA ABC-type triblock copolymers: toward the construction of nanostructures in epoxy thermosets. Polymer Chemistry, 9(48):5644–5654.
19. Jiang X, Luo S, Armes SP, Shi W, Liu S, 2006. UV irradiation-induced shell cross-linked micelles with pH-responsive cores using ABC triblock copolymers. Macromolecules, 39(18):5987–5994.
20. Keefe BJO, Monnier SM, Hillmyer MA, Tolman WB, Se PS, 2001. Rapid and Controlled Polymerization of Lactide by Structurally Characterized Ferric Alkoxides. Journal of the American Chemical Society, 123(2):339–340.
21. Ko BT, Lin CC, 2001. Synthesis, characterization, and catalysis of mixed-ligand lithium aggregates, excellent initiators for the ring-opening polymerization of L-lactide. Journal of the American Chemical Society, 123(33):7973–7977.
22. Kryuchkov MA, Detrembleur C, Bazuin CG, 2014. Linear amphiphilic diblock copolymers of lactide and 2-dimethylaminoethyl methacrylate using bifunctional-initiator and one-pot approaches. Polymer, 55(10):2316–2324.
23. Lee H, Matyjaszewski K, Yu S, Sheiko SS, 2005. Molecular brushes with spontaneous gradient by atom transfer radical polymerization. Macromolecules, 38(20):8264–8271.
24. Lei L, Li F, Zhao H, Wang Y, 2018. One-pot synthesis of block copolymers by ring-opening polymerization and ultraviolet light-induced ATRP at ambient temperature. Journal of Polymer Science, Part A: Polymer Chemistry, 56(7):699–704.
25. Li WJ, Danielson KG, Alexander PG, Tuan RS, 2003. Biological response of chondrocytes cultured in three-dimensional nanofibrous poly(ε-caprolactone) scaffolds. Journal of Biomedical Materials Research - Part A, 67(4):1105–1114.
26. Liu Y, Huang G, Pang Y, Han M, Ji S, 2015. One-pot synthesis of thermoresponsive cellulose-based miktoarm graft copolymer by simultaneous ATRP and ROP. Journal of Renewable Materials, 3(2):113–119.
27. Luan B, Yuan Q, Pan CY, 2004. Synthesis and Characterization of Poly(trimethylene oxide)-block-Polystyrene and Poly(trimethylene oxide)-block-Polystyrene-block-Poly(methyl methacrylate) by Combination of Atom Transfer Radical Polymerization (ATRP) and Cationic Ring-Opening Polymerization (CROP). Macromolecular Chemistry and Physics, 205(15):2097–2104.
28. Ma Z, Yu H, Jiang W, 2009. Bump-surface multicompartment micelles from a linear ABC triblock copolymer: A combination study by experiment and computer simulation. Journal of Physical Chemistry B, 113(11):3333–3338.
29. Mahajan S, Cho BK, Allgaier J, Fetters LJ, Coates GW, Wiesner U, 2004. Synthesis of amphiphilic ABC triblock copolymers with PEO as the middle block. Macromolecular Rapid Communications, 25(22):1889–1894.
30. Messman JM, Scheuer AD, Storey RF, 2005. Synthesis and characterization of A-B-A triblock copolymers derived from chloro-telechelic poly(l-lactide): Combining ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). Polymer, 46(11):3628–3638.
31. Moad G, Chong YK, Postma A, Rizzardo E, Thang SH, 2005. Advances in RAFT polymerization:The synthesis of polymers with defined end-groups. Polymer, 46(19):8458–8468.
32. Nartop D, Hasanoğlu ÖE, Gündem M, Çeker S, Ağar G, Öğütçü H, Sarı N, 2019. Synthesis, antimicrobial and antimutagenic effects of novel polymeric-Schiff bases including indol. Journal of Molecular Structure 1195:877-882.
33. Öztürk T, Göktaş M, Hazer B, 2010. Synthesis and characterization of poly(methyl methacrylate-block-ethylene glycol-block-methyl methacrylate) block copolymers by reversible addition-fragmentation chain transfer polymerization. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 48(1):65–70.
34. Öztürk T, Yavuz M, Göktaş M, Hazer B, 2016. One-step synthesis of triarm block copolymers by simultaneous atom transfer radical and ring-opening polymerization. Polymer Bulletin, 73(6):1497–1513.
35. Palacios JK, Tercjak A, Liu G, Wang D, Zhao J, Hadjichristidis N, Müller AJ, 2017. Trilayered Morphology of an ABC Triple Crystalline Triblock Terpolymer. Macromolecules, 50(18), 7268–7281.
36. Persson PV, Casas J, Iversen T, Córdova A, 2006. Direct organocatalytic chemoselective synthesis of a dendrimer-like star polyester. Macromolecules, 39(8):2819–2822.
37. Şanal T, Oruç O, Öztürk T, Hazer B, 2015. Synthesis of pH- and thermo-responsive poly (ε-caprolactone-b-4-vinyl benzyl-g-dimethyl amino ethyl methacrylate) brush type graft copolymers via RAFT polymerization. Journal of Polymer Research, 22(3):1-12.
38. Sivalingam G, Vijayalakshmi SP, Madras G, 2004. Enzymatic and thermal degradation of poly(ε-caprolactone), poly(D,L-lactide), and their blends. Industrial and Engineering Chemistry Research, 43(24):7702–7709.
39. Villarroya S, Zhou J, Thurecht KJ, Howdle SM, 2006. Synthesis of graft copolymers by the combination of ATRP and enzymatic ROP in scCO2. Macromolecules, 39(26):9080–9086.
40. Wang C, Hsiue G, 2005. Polymer-DNA Hybrid Nanoparticles Based on Folate-Polyethylenimine-block-poly(L-lactide). Bioconjugate Chemistry, 16(2):391–396.
41. Wang F, Bronich TK, Kabanov AV, Rauh RD, Roovers J, 2008. Synthesis and characterization of star poly(ε-caprolactone)-b-poly(ethylene glycol) and poly(L-lactide)-b-poly(ethylene glycol) copolymers: Evaluation as drug delivery carriers. Bioconjugate Chemistry, 19(7):1423–1429.
42. Wang JL, Wang LU, Dong CM, 2005. Synthesis, crystallization, and morphology of star-shaped poly(ε-caprolactone). Journal of Polymer Science, Part A: Polymer Chemistry, 43(22):5449–5457.
43. Wang JS, Matyjaszewski K, 1995. Controlled/“Living” Radical Polymerization. Atom Transfer Radical Polymerization in the Presence of Transition-Metal Complexes. Journal of the American Chemical Society, 117(20):5614–5615.
44. Wolf FF, Friedemann N, Frey H, 2009. Poly(lactide)-block-poly(HEMA) Block Copolymers: An orthogonal one-pot combination of ROP and ATRP, using a bifunctional initiator. Macromolecules, 42(15):5622-5628.
45. Xie M, Dang J, Han H, Wang W, Liu J, He X, Zhang Y, 2008. Well-defined brush copolymers with high grafting density of amphiphilic side chains by combination of ROP, ROMP, and ATRP. Macromolecules, 41(23):9004–9010.
46. Ydens I, Degée P, Dubois P, Libiszowski J, Duda A, Penczek S, 2003. Combining ATRP of methacrylates and ROP of L,L-dilactide and ε-caprolactone. Macromolecular Chemistry and Physics, 204(1):171–179.
47. Yilmaz G, 2019. One-pot synthesis of star copolymers by the combination of metal-free ATRP and ROP processes. Polymers, 11(10):1–9.
48. Yu YC, Li G, Kang HU, Youk JH, 2012. One-step synthesis of poly(alkyl methacrylate)-b-polyester block copolymers via a dual initiator route combining RAFT polymerization and ROP. Colloid and Polymer Science, 290(16):1707–1712.
49. Zhai X, Peleshanko S, Klimenko NS, Genson KL, Vaknin D, Vortman MY, Shevchenko VV, Tsukruk VV, 2003. Amphiphilic dendritic molecules: Hyperbranched polyesters with alkyl-terminated branches. Macromolecules, 36(9):3101–3110.
50. Zhu J, Jiang W, 2005. Self-assembly of ABC triblock copolymer into giant segmented wormlike micelles in dilute solution. Macromolecules, 38(22):9315–9323.