Synthesis of poly[ε-caprolacton-b-epichlorohydryin-b-ε-caprolactone]- g-poly(styrene) Block-Graft Copolymers via Cationic Ring Opening and Atom Transfer Radical Polymerization Transformations

Yıl 2017, Cilt: 7 Sayı: 3, 161 - 169, 30.09.2017

ÜMİT Yıldıko İsmail Çakmak Temel Öztürk Abdulkadir Yörük

Öz

The poly[(ε-caprolacton-b-epichlorohydrin-b-ε-caprolactone)]-g-(polystyrene-) [(PCL-b-ECH-bPCL)]-g-PS block-graft copolymers were prepared via cationic, ring opening (ROP) and atom transfer radical
polymerization (ATRP) transformations. With this goal in the frst, cationic ring-opening technique was used to
polymerize the epichlorohydrin (ECH). The ring opening polymerisation (ROP) of ε-caprolactone (ε-CL) was
carried out using poly (epichlorohydrin) (PECH) with hydroxyl functional groups acting as initiators at 110 ºC to
yield poly(ε-caprolacton-b-epichlorohydrin-b-ε-caprolactone) (PCL-PECH-PCL) block copolymer. Finally, in the
atom transfer radical polymerisation (ATRP) of the styrene, chloromethyl groups of the PECH segment of PCLPECH-PCL were used as the starting functional group. [PCL-b-PECH-b-CL] -g-PS graft copolymer block was
obtained as a result of polymerization. The results of the analysis indicated that the molecular weights of the graft
copolymers increased linearly with styrene polymerisation. Synthesized polymers were characterized by 1 H-NMR,
GPC and DSC techniques.

Anahtar Kelimeler

ATRP, ROP, block copolymer, block-graft copolymer, epichlorohydrin, ε-caprolacton.

Poli - [(ε-kaprolakton-b-epiklorohidrin-b-ε-kaprolakton)] - g- (polistiren-) [(PCL-b-ECH-b-PCL)] - g-PS Blok-aşı Kopolimerleri Katyonik, Halka Açıklma Polimerizasyonu (ROP) ve Atom Transfer Radikal Polimerizasyon (ATRP) Tekniklerinin Kombinasyonu ile Sentezi

Öz

Poli - [(ε-kaprolakton-b-epiklorohidrin-b-ε-kaprolakton)] - g- (polistiren -) [(PCL-b-ECH-b-PCL)] - g-PS
blok-aşı kopolimerleri katyonik, halka açıklama polimerizasyonu (ROP) ve atom transfer radikal polimerizasyon
(ATRP) tekniklerinin kombinasyonu ile sentezlenmiştir. Bu amaçla, epiklorohidrin (ECH) polimerize etmek
için katyonik halka açma tekniği kullanılmıştır. Sentezlenen, Hidroksil fonksiyonel gruplu poli (epiklorohidrin)
(PECH), ε-kaprolaktonun (ε-CL) 110 ° C’de halkalı açılma polimerizasyonunun (ROP) başlatıcısı olarak poli
(ε-kaprolakton-b-epiklorohidrin- B-ε-kaprolakton) (PCL-PECH-PCL) blok kopolimerinin eldesinde kullanıldı.
Son olarak, başlatıcı olarak PCL-PECH-PCL’nin PECH bloğunun klorometil gruplarını kullanarak gerçekleştirilen
stirenin atom transfer radikal polimerizasyonu (ATRP), [PCL-b-PECH-b-CL] -g-PS-graft kopolimeri oluşumuyla
sonuçlanmıştır. Elde edilen sonuçlar, graft kopolimerlerinin moleküler ağırlıklarının stiren dönüşümüyle arttığını
gösterdi. Polimerler, 1H-NMR, GPC ve DSC teknikleri ile karakterize edildi.

Anahtar Kelimeler

ATRP, ROP, blok kopolimer, blok-aşı kopolimer, epiklorohidrin, ε-kaprolakton.

Kaynakça

• Alam BM, Aouak T, Alandis NM, Alam MM. Synthesis, Characterization, Drug Solubility Enhancement, and Drug Release Study of Poly(Methacrylic Acid-graft-Simvastatin). Int. J. Polym. Mater. Polym. Biomater. 2015;64:229–241.
• Braunecker WA, Brown WC, Morelli BC, Tang W, Poli R, Matyjaszewski K. Origin of Activity in Cu-, Ru-, and Os-Mediated Radical Polymerization Macromolecules. 2007;40:8576–8585.
• Cakmak I, Baykara H, Set B. Synthesis of poly(epichlorohydrin-g-methyl methacrylate) and poly(epichlorohydrin-g-styrene) graft copolymers by a combination of cationic and photopolymerization methods. J. Appl. Polym. Sci. 2008;107:1604–1608
• Cakmak I, Baykara H. Synthesis of poly(epichlorohydrin-g-methyl methacrylate) graft copolymers by the combination of cationic and atom transfer radical polymerization.) J. Appl. Polym. Sci. 2006;102:2725–2729.
• Chen G, Pei X, Wei H, Xu L, Fang X. Synthesis and characterization of sulfonated block copolyimides derived from 4,4'-sulfide-bis(naphthalic anhydride) for proton exchange membranes. J. Appl. Polym. Sci. 2015;132:41501.
• Chen M-Z, Sun H-M, Li W-F, Wang Z-G, Shen Q, Zhang Y. Synthesis, structure of functionalized N-heterocyclic carbene complexes of Fe(II) and their catalytic activity for ring-opening polymerization of ε-caprolactone. J. Organomet. Chem. 2006;691:2489–2494.
• Cho I. New ring-opening polymerizations for copolymers having controlled microstructures. Prog. Polym. Sci. 2000;25:1043–1087.
• Coessens V, Pintauer T, Matyjaszewski K. Functional polymers by atom transfer radical polymerization. Prog. Polym. Sci. 2001;26:337–377
• Erdogan T, Bernaerts KV, Van Renterghem LM, Du Prez FE, Goethals EJ. Preparation of star block co-polymers by combination of cationic ring opening polymerization and atom transfer radical polymerization. Des. Monomers Polym. 2005;8:705–714.
• Gowda RR, Chakraborty D. Environmentally benign process for bulk ring opening polymerization of lactones using iron and ruthenium chloride catalysts. J. Mol. Catal. -Chem. 2009;301:84–92.
• Kato M, Kamigaito M, Sawamoto M, Higashimura T. Polymerization of Methyl Methacrylate with the Carbon Tetrachloride / Dichlorotris- triphenylphosphine) ruthenium(II) / Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization. Macromolecules. 1995;28:1721–1723.
• Matyjaszewski K. Radical Nature of Cu-Catalyzed Controlled Radical Polymerizations (Atom Transfer Radical Polymerization) Macromolecules. 1998;31:4710–4717.
• Messman JM, Scheuer AD, Storey RF. 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. 2005;46:3628–3638.
• Muftuoglu A. E, Cianga I, Colak D, YagciY, Synthesis of A2B and A2B2 type miktoarm star co-polymers by combination of ATRP or ROP with photoinduced radical polymerization. Designed Monomers and Polymers. 2004;7:563-582.
• Nuyken O, Weidner R. Graft and block copolymers via polymeric azo initiators () Adv. Polym. Sci. 1986;73-74:145–199.
• Okcu SS, Durmaz YY, Yagci Y, Synthesis and Characterization of Telechelic Block Co-polymers by Combination of Atom Transfer Radical Polymerization and Click Chemistry Processes. Designed Monomers and Polymers. 2010;13:459-472.
• Okrasa L, Pakula T, Inoue Y, Matyjaszewski K. Morphology and thermomechanical properties of well-defined polyethylene-graft-poly(n-butyl acrylate) prepared by atom transfer radical polymerization. Colloid Polym. Sci. 2004;282:844–853.
• Percec V, Barboiu B. "Living" Radical Polymerization of Styrene Initiated by Arenesulfonyl Chlorides and CuI(bpy)nCl. Macromolecules. 1995;2823:7970–7972.
• Stoeckel N, Wieland PC, Nuyken O. New syntheses of graft copolymers using the DPE-technique: ATRP graft copolymerization. Polym. Bull. 2002;49:243–250.
• Stridsberg KM, Ryner M, Albertsson AC. Controlled Ring-Opening Polymerization: Polymers with designed Macromolecular Architecture. In Degradable Aliphatic Polyesters, ed AC Albertsson. 2002;157:41–65. Berlin: Springer-Verlag Berlin.
• Szabó Á, Wacha A, Thomann R, Szarka G, Bóta A, Iván B. Synthesis of Poly(methyl methacrylate)-poly(poly(ethylene glycol) methacrylate)-polyisobutylene ABCBA Pentablock Copolymers by Combining Quasiliving Carbocationic and Atom Transfer Radical Polymerizations and Characterization. J. Macromol. Sci. Part A. 2015;52:252–259.
• Tasdelen MA, Yagci Y, Demirel AL, Biedron T, Kubisa P. Synthesis and Characterization of Block-Graft Copolymers [poly(epichlorohydrin-b-styrene)-g-poly(methyl methacrylate)] by Combination of Activated Monomer Polymerization, NMP and ATRP). Polym. Bull. 2007;58:653–663.
• Tsarevsky NV, Braunecker WA, Tang W, Brooks SJ, Matyjaszewski K, et al. Copper-based ATRP catalysts of very high activity derived from dimethyl cross-bridged cyclam. J. Mol. Catal. Chem. 2006;257:132–140.
• Wang J, Matyjaszewski K. Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes. J. Am. Chem. Soc. 1995;117:5614–5615.
• Wang J, Matyjaszewski K. Controlled/"Living" Radical Polymerization. Halogen Atom Transfer Radical Polymerization Promoted by a Cu(I)/Cu(II) Redox Process. Macromolecules. 1995;28:7901–7910.
• Yang L, Zhou H, Shi G, Wang Y, Pan C-Y. Synthesis of ABCD 4-miktoarm star polymers by combination of RAFT, ROP, and “Click Chemistry”. () J. Polym. Sci. Part -Polym. Chem. 2008;46:6641–6653.
• Yao W, Mu Y, Gao A, Su Q, Liu Y, Zhang Y. Efficient ring-opening polymerization of ɛ-caprolactone using anilido-imine–aluminum complexes in the presence of benzyl alcohol Polymer. 2008;49:2486–2491.
• Yuan W, Yuan J, Zhou M, Pan C. Synthesis, characterization, and fluorescence of pyrene-containing eight-arm star-shaped dendrimer-like copolymer with pentaerythritol core. J. Polym. Sci. Part -Polym. Chem. 2008;46:2788–2798.