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Polymer Bulletin

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20.11.2015 | Original Paper

One-step synthesis of triarm block copolymers by simultaneous atom transfer radical and ring-opening polymerization

verfasst von: Temel Öztürk, Mahmut Yavuz, Melahat Göktaş, Baki Hazer

Erschienen in: Polymer Bulletin | Ausgabe 6/2016

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Abstract

One-step synthesis of poly(MMA-b-CL) triarm block copolymers was carried out by atom transfer radical polymerization of methyl methacrylate (MMA) and ring-opening polymerization of ε-caprolactone (CL) using 3-chloro-1,2-propanediol trifunctional initiator. The triarm block copolymers comprising one poly-MMA arm and two poly-CL arms were synthesized by changing some polymerization conditions such as monomer/initiator concentration, polymerization time. The effect of the reactions conditions on the polydispersity and molecular weights was also investigated. The block lengths of the block copolymers were calculated by using ¹H-nuclear magnetic resonance (¹H-NMR) spectrum. It was observed that the block length could be altered by varying the monomer and initiator concentrations. The characterization of the products was achieved by using ¹H-NMR, Fourier-transform infrared spectroscopy, gel-permeation chromatography, differential scanning calorimetry, thermogravimetric analysis and fractional precipitation techniques.

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Wang JS, Matyjaszewski K (1995) Controlled living radical polymerization: atom-transfer radical polymerization in the presence of transition-metal complexes. J Am Chem Soc 117:5614–5615. doi:10.1021/ja00125a035 CrossRef

Kato M, Kamigaito M, Sawomoto M, Higashimura T (1995) Polymerization of methyl-methacrylate with the carbon-tetrachloride dichloro tris(triphenylphosphine)ruthenium(II) methyl aluminum bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization. Macromolecules 28:1721–1723. doi:10.1021/ma00109a056 CrossRef

Haddleton DM, Waterson C, Derrick PJ, Jasieczek CB, Shooter AJ (1997) Monohydroxy terminally functionalised poly(methyl methacrylate) from atom transfer radical polymerisation. Chem Commun 7:683–684. doi:10.1039/a700677b CrossRef

Lee HI, Matyjaszewski K, Yu S, Sheiko SS (2005) Molecular brushes with spontaneous gradient by atom transfer radical polymerization. Macromolecules 38:8264–8271. doi:10.1021/ma051231z CrossRef

Kruk M, Dufour B, Celer EB, Kowalewski T, Jaroniec M, Matyjaszewski K (2005) Synthesis of mesoporous carbons using ordered and disordered mesoporous silica templates and polyacrylonitrile as carbon precursor. Phys Chem B 109:9216–9225. doi:10.1021/jp045594x CrossRef

Hawker CJ, Bosman AW, Harth E (2001) New polymer synthesis by nitroxide mediated living radical polymerizations. Chem Rev 101:3661–3688. doi:10.1021/cr990119u CrossRef

Lessard B, Maric M (2008) Nitroxide-mediated synthesis of poly(poly(ethylene glycol) acrylate) (PPEGA) comb-like homopolymers and block copolymers. Macromolecules 41:7870–7880. doi:10.1021/ma800603a CrossRef

Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad E, Rizzardo E, Thang SH (1998) Living free-radical polymerization by reversible addition-fragmentation chain transfer: the RAFT process. Macromolecules 31:5559–5562. doi:10.1021/ma9804951 CrossRef

Ozturk T, Hazer B (2010) Synthesis and characterization of a novel macromonomer initiator for reversible addition fragmentation chain transfer (RAFT). Evaluation of the polymerization kinetics and gelation behaviors. J Macromol Sci Part A Pure Appl Chem 47:265–272. doi:10.1080/10601320903527095 CrossRef

10.

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. J Polym Res 22:3–15. doi:10.1007/s10965-014-0640-z CrossRef

11.

Moad G, Chong YK, Postma A, Rizzardo E, Thang SH (2005) Advances in RAFT polymerization: the synthesis of polymers with defined end-groups. Polymer 46:8458–8468. doi:10.1016/j.polymer.2004.12.061 CrossRef

12.

Perrier S, Davis TP, Carmichael AJ, Haddleton DM (2003) Reversible addition-fragmentation chain transfer polymerization of methacrylate, acrylate and styrene monomers in 1-alkyl-3-methylimidazolium hexafluoro phosphate. Eur Polym J 39:417–422. doi:10.1016/S0014-3057(02)00250-1 CrossRef

13.

Barner Kowollik C, Quinn JF, Morsley DR, Davis TP (2001) Modeling the reversible addition-fragmentation chain transfer process in cumyldithiobenzoate-mediated styrene homo polymerizations: assessing rate coefficients for the addition-fragmentation equilibrium. J Polym Sci Part A: Polym Chem 39:1353–1365. doi:10.1002/pola.1112 CrossRef

14.

Ray B, Isobe Y, Matsumoto K, Habaue S, Okamoto Y, Kamigaito M, Sawamoto M (2004) RAFT polymerization of N-isopropylacrylamide in the absence and presence of Y(OTf)(3): simultaneous control of molecular weight and tacticity. Macromolecules 37:1702–1710. doi:10.1021/ma035119h CrossRef

15.

Patton DL, Advincula RC (2006) A versatile synthetic route to macromonomers via RAFT polymerization. Macromolecules 39:8674–8683. doi:10.1021/ma061382h CrossRef

16.

Öztürk T, Göktaş M, Hazer B (2011) Synthesis and characterization of poly(methyl methacrylate-block-ethylene glycol-block-methyl methacrylate) block copolymers by reversible addition fragmentation chain transfer polymerization. J Macromol Sci Part A Pure Appl Chem 48:65–72. doi:10.1080/10601325.2011.528310 CrossRef

17.

Öztürk T, Göktaş M, Hazer B (2010) One-step synthesis of triarm block copolymers via simultaneous reversible-addition fragmentation chain transfer and ring-opening polymerization. J Appl Polym Sci 117:1638–1645. doi:10.1002/app.32031

18.

Öztürk T, Atalar MN, Göktaş M, Hazer B (2013) One-step synthesis of block-graft copolymers via simultaneous reversible-addition fragmentation chain transfer and ring-opening polymerization using a novel macroinitiator. J Polym Sci Part A: Polym Chem 51:2651–2659. doi:10.1002/pola.26654 CrossRef

19.

Öztürk T, Göktaş M, Savaş B, Işıklar M, Atalar MN, Hazer B (2014) Synthesis and characterization of poly(vinylchloride-graft-2-vinylpyridine) graft copolymers using a novel macroinitiator by reversible addition-fragmentation chain transfer polymerization. e-Polymers 14:27–34. doi:10.1515/epoly-2013-0011 CrossRef

20.

Wang JS, Matyjaszewski K (1995) Controlled living radical polymerization—halogen atom-transfer radical polymerization promoted by a Cu(I)Cu(Ii) redox process. Macromolecules 28:7901–7910. doi:10.1021/ma00127a042 CrossRef

21.

Patten TE, Matyjaszewski K (1998) Atom transfer radical polymerization and the synthesis of polymeric materials. Adv Mater 10:901–915. doi:10.1002/(SICI)1521-4095(199808)10:12<901:AID-ADMA901>3.3.CO;2-2 CrossRef

22.

Zhang H, Lei X, Su Z, Liu P (2007) A novel method of surface-initiate atom transfer radical polymerization of styrene from silica nanoparticles for preparation of mono dispersed core-shell hybrid nanospheres. J Polym Res 14:253–260. doi:10.1007/s10965-007-9104-z CrossRef

23.

Yagci Y, Schnabel W (1990) Light-induced synthesis of block and graft copolymers. Prog Polym Sci 15:551–601. doi:10.1016/0079-6700(90)90006-M CrossRef

24.

Ruzette AV, Leibler L (2005) Block copolymers in tomorrow’s plastics. Nat Mater 4:19–31. doi:10.1038/nmat1295 CrossRef

25.

Shipp DA, Wang J, Matyjaszewski K (1998) Synthesis of acrylate and methacrylate block copolymers using atom transfer radical polymerization. Macromolecules 31:8005–8008. doi:10.1021/ma981033q CrossRef

26.

Bates FM, Fredrickson GH (1990) Block copolymer thermodynamics: theory and experiment. Ann Rev Phys Chem 41:525–557. doi:10.1146/annurev.pc.41.100190.002521 CrossRef

27.

Bilalis P, Pitsikalis M, Hadjichristidis N (2006) Controlled nitroxide mediated and reversible addition-fragmentation chain transfer polymerization of N-vinylpyrrolidone: synthesis of block copolymers with styrene and 2-vinylpyridine. J Polym Sci Part A Polym Chem 44:659–665. doi:10.1002/pola.21198 CrossRef

28.

Noshay A, Mcgrath JE (1977) Block copolymers, overview and critical survey. Academic Press, New York

29.

Makarova LI, Filimonova LV, Dubrovina LV, Buzin MI, Nikiforova GG, Zavin BG, Papkov VS (2010) Synthesis and properties of siloxane(ethylene oxide) urethane block copolymers. Polym Sci Ser B 52:346–352. doi:10.1134/S1560090410050118 CrossRef

30.

Vinchon Y, Reeb R, Riess G (1976) Preparation of macromolecular azo initiators by anionic-polymerization: application to synthesis of block copolymers. Eur Polym J 12:317–321CrossRef

31.

Peng ZP, Wang D, Liu X, Tong Z (2007) RAFT synthesis of a water-soluble triblock copolymer of poly(styrenesulfonate)-b-poly(ethylene glycol)-b-poly(styrenesulfonate) using a macromolecular chain transfer agent in aqueous solution. J Polym Sci Part A Polym Chem 45:3698–3706. doi:10.1002/pola.22119 CrossRef

32.

Yoshikawa C, Goto A, Tsujii Y, Fukuda T, Yamamoto K, Kishida A (2005) Fabrication of high-density polymer brush on polymer substrate by surface-initiated living radical polymerization. Macromolecules 38:4604–4610. doi:10.1021/ma047556h CrossRef

33.

Baum M, Brittain WJ (2002) Synthesis of polymer brushes on silicate substrates via reversible addition fragmentation chain transfer technique. Macromolecules 35:610–615. doi:10.1021/ma0112467 CrossRef

34.

Shinoda H, Matyjaszewski K (2001) Improving the structural control of graft copolymers. Copolymerization of poly (dimethyl siloxane) macromonomer with methyl methacrylate using RAFT polymerization. Macromol Rapid Commun 22:1176–1181. doi:10.1002/1521-3927(20011001)22:14<1176:AID-MARC1176>3.0.CO;2-J CrossRef

35.

Lord HT, Quinn JF, Angus SD, Whittaker MR, Stenzel MH, Davis TP (2003) Micro gel stars via reversible addition fragmentation chain transfer (RAFT) polymerisation: a facile route to macro porous membranes, honeycomb patterned thin films and inverse opal substrates. J Mater Chem 13:2819–2824. doi:10.1039/b304208c CrossRef

36.

Chen M, Ghiggino KP, Launikonis A, Mau AWH, Rizzardo E, Sasse WHF, Thang SH, Wilson GJ (2003) RAFT synthesis of linear and star-shaped light harvesting polymers using di- and hexafunctional ruthenium polypyridine reagents. J Mater Chem 13:2696–2700. doi:10.1039/b303576j CrossRef

37.

Roy D, Guthrie JT, Perrier S (2005) Graft polymerization: grafting poly(styrene) from cellulose via reversible addition-fragmentation chain transfer (RAFT) polymerization. Macromolecules 38:10363–13372. doi:10.1021/ma0515026 CrossRef

38.

Bosman AW, Vestberg R, Heumann A, Frechet JMJ, Hawker CJJ (2003) A modular approach toward functionalized three-dimensional macromolecules: from synthetic concepts to practical applications. Am Chem Soc 125:715–728. doi:10.1021/ja028392s CrossRef

39.

Haraguchi N, Hirao A (2003) Synthesis of well-defined star-linear block polystyrenes by coupling reaction of chain-functionalized polystyrenes with a definite number of benzyl bromide moieties with polystyryllithiums. Macromolecules 36:9364–9372. doi:10.1021/ma034799l CrossRef

40.

Li Z, Hillmyer MA, Lodge TP (2004) Synthesis and characterization of triptych mu-ABC star triblock copolymers. Macromolecules 37:8933–8940. doi:10.1021/ma048607d CrossRef

41.

Fragouli PG, Iatrou H, Hadjichristidis N, Sakurai T, Hirao A (2006) Synthesis and characterization of model 3-miktoarm star copolymers of poly(dimethylsiloxane) and poly(2-vinylpyridine). J Polym Sci Polym Chem 44:614–619. doi:10.1002/pola.21197 CrossRef

42.

Hazer B (1991) Synthesis of styrene-tetrahydrofuran branched block copolymers. Eur Polym J 27:975–978. doi:10.1016/0014-3057(91)90043-N CrossRef

43.

Le Hellaye M, Lefay C, Davis TP, Stenzel MH, Barner- Kowollik C (2008) Simultaneous reversible addition fragmentation chain transfer and ring-opening polymerization. J Polym Sci Part A Polym Chem 46:3058–3067. doi:10.1002/pola.22647 CrossRef

44.

Hong J, Wang Q, Fan Z (2006) Synthesis of multiblock polymer containing narrow polydispersity blocks. Macromol Rapid Commun 27:57–62. doi:10.1002/marc.200500678 CrossRef

45.

Cheng C, Khoshdel E, Wooley KL (2007) One-pot tandem synthesis of a core: shell brush copolymer from small molecule reactants by ring-opening metathesis and reversible addition-fragmentation chain transfer (co)polymerizations. Macromolecules 40:2289–2292. doi:10.1021/ma0627525 CrossRef

46.

Mahanthappa MK, Bates FS, Hillmyer MA (2005) Synthesis of ABA triblock copolymers by a tandem ROMP-RAFT strategy. Macromolecules 38:7890–7894. doi:10.1021/ma051535l CrossRef

47.

Mori H, Masuda S, Endo T (2008) Ring-opening copolymerization of 10-methylene-9,10-dihydroanthryl-9-spirophenylcyclopropane via free radical and RAFT processes. Macromolecules 41:632–639. doi:10.1021/ma0714262 CrossRef

48.

Han DH, Pan CY (2007) Preparation and characterization of heteroarm H-shaped terpolymers by combination of reversible addition-fragmentation transfer polymerization and ring-opening polymerization. J Polym Sci Part A Polym Chem 45:789–799. doi:10.1002/pola.21907 CrossRef

49.

Xu XQ, Jia ZF, Sun RM, Huang JL (2006) Synthesis of well-defined, brush-type, amphiphilic [poly(styrene-co-2-hydroxyethyl methacrylate)-graft-poly(epsilon-caprolactone)]-b-poly(ethylene oxide)-b-[poly(styrene-co-2-hydroxyethyl methacrylate)-graft-poly(epsilon-caprolactone)] and its aggregation behavior in aqueous media. J Polym Sci Part A: Polym Chem 44:4396–4408. doi:10.1002/pola.21549 CrossRef

50.

Xu XW, Huang JL (2006) Synthesis and characterization of amphiphilic copolymer of linear poly(ethylene oxide) linked with [poly(styrene-co-2-hydroxyethyl methacrylate)graft-poly(epsilon-caprolactone)] using sequential controlled polymerization. J Polym Sci Part A Polym Chem 44:467–476. doi:10.1002/pola.21162 CrossRef

51.

Liu J, Pan CY (2005) Synthesis and characterization of H-shaped copolymers by combination of RAFT polymerization and CROP. Polymer 46:11133–11141. doi:10.1016/j.polymer.2005.08.072 CrossRef

52.

Wang WP, You YZ, Hong CY, Xu J, Pan CY (2005) Synthesis of comb-shaped copolymers by combination of reversible addition-fragmentation chain transfer polymerization and cationic ring-opening polymerization. Polymer 46:9489–9494. doi:10.1016/j.polymer.2005.07.037 CrossRef

53.

Shi PJ, Li YG, Pan CY (2004) Block and star block copolymers by mechanism transformation: X. Synthesis of poly(ethylene oxide) methyl ether/polystyrene/poly(L-lactide) ABC miktoarm star copolymers of by combination of RAFT and ROP. Eur Polym J 40:1283–1290. doi:10.1016/j.europolymj.2004.02.024 CrossRef

54.

You Y, Hong C, Wang W, Lu W, Pan CY (2004) Preparation and characterization of thermally responsive and biodegradable block copolymer comprised of PNIPAAM and PLA by combination of ROP and RAFT methods. Macromolecules 37:9761–9767. doi:10.1021/ma048444t CrossRef

55.

Chang C, Wei H, Quan CY, Li YY, Liu J, Wang ZC, Cheng SX, Zhang XZ, Zhuo RX (2008) Fabrication of thermosensitive PCL-PNIPAAm-PCL triblock copolymeric micelles for drug delivery. J Polym Sci Part A: Polym Chem 46:3048–3057. doi:10.1002/pola.22645 CrossRef

56.

Luan B, Zhang BQ, Pan CY (2006) Synthesis and characterizations of well-defined branched polymers with AB(2) branches by combination of RAFT polymerization and ROP as well as ATRP. J Polym Sci Part A: Polym Chem 44:549–560. doi:10.1002/pola.21183 CrossRef

57.

Schmid C, Falkenhagen J, Barner-Kowollik C (2011) An efficient avenue to poly(styrene)-block-poly(epsilon-caprolactone) polymers via switching from RAFT to hydroxyl functionality: synthesis and characterization. J Polym Sci Part A: Polym Chem 49:1–10. doi:10.1002/pola.24299 CrossRef

58.

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 Polym Sci 290:1707–1712. doi:10.1007/s00396-012-2788-6 CrossRef

59.

Farah AA, Hall N, Morin S, Pietro W-J (2006) Poly(epsilon-caprolactone)-block-polystyrene metallopolymers via sequential ROP and ATRP condition with in situ generated ruthenium catalyst. Polymer 47:4282–4291. doi:10.1016/j.polymer.2006.03.037 CrossRef

60.

Deng G, Zhang L, Liu C, He L, Chen Y (2005) Synthesis of miktoarm star (block) polymers based on a heterofunctional initiator via combination of ROP, ATRP and functional group transformation. Eur Polym J 41:1177–1186. doi:10.1016/j.eurpolymj.2005.01.003 CrossRef

61.

Tao L, Luan B, Pan C-Y (2003) Block and star block copolymers by mechanism transformation. VIII Synthesis and characterization of triblock poly(LLA-b-St-b-MMA) by combination of ATRP and ROP. Polymer 44:1013–1020. doi:10.1016/S0032-3861(02)00870-4 CrossRef

62.

Messman J-M, Scheuer A-D, Storey R-F (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 46:3628–3638. doi:10.1016/j.polymer.2005.03.023 CrossRef

63.

Göktaş M, Öztürk T, Atalar MN, Tekeş AT, Hazer B (2014) One-step synthesis of triblock copolymers via simultaneous reversible-addition fragmentation chain transfer (RAFT) and ring-opening polymerization using a novel difunctional macro-RAFT agent based on polyethylene glycol. J Macromol Sci Part A 51:854–863. doi:10.1080/10601325.2014.953366 CrossRef

64.

Hazer B, Erdem B, Lenz RW (1994) Styrene polymerization with some new macro or macromonomeric azo initiators having PEG units. J Polym Sci Part A: Polym Chem 32:1739–1746. doi:10.1002/pola.1994.080320916 CrossRef

65.

Wu B, Lenz RW, Hazer B (1999) Polymerization of methyl methacrylate and its copolymerization with epsilon-caprolactone catalyzed by isobutylalumoxane catalyst. Macromolecules 32:6856–6859. doi:10.1021/ma990166o CrossRef

66.

Shuster M, Narkis M, Siegmann A (1994) Polymeric antiplasticization of polycarbonate with polycaprolactone. Polym Eng Sci 34:1613–1618. doi:10.1002/pen.760342106 CrossRef

67.

Huarng JC, Min KS, White JL (1988) Phase-equilibrium in the binary and ternary blend system—polycaprolactone-polyvinyl chloride-styrene acrylonitrile copolymer. Polym Eng Sci 28:1590–1599. doi:10.1002/pen.760282404 CrossRef

68.

Brandrup J, Immergut EH, Grulke EA (2003) Polymer handbook, 4th edn. Wiley, New York

Titel: One-step synthesis of triarm block copolymers by simultaneous atom transfer radical and ring-opening polymerization
verfasst von: Temel Öztürk
Mahmut Yavuz
Melahat Göktaş
Baki Hazer
Publikationsdatum: 20.11.2015
Verlag: Springer Berlin Heidelberg
Erschienen in: Polymer Bulletin / Ausgabe 6/2016
Print ISSN: 0170-0839
Elektronische ISSN: 1436-2449
DOI: https://doi.org/10.1007/s00289-015-1558-2

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