Alifatik Ester-Eter Yapılı Yeni Makromonomerlerin Sentezi ve “Dolaylı Aşılama” Stratejisinde Kullanımı

Yıl 2024, Cilt: 14 Sayı: 3, 1471 – 1485, 15.09.2024

Efkan Çatıker , Temel Öztürk

https://doi.org/10.31466/kfbd.1475630

Öz

Bu çalışmada, poli(akrilik asit-g-hidroksietil akrilat) (PAA-g-PHEA) ve poli(akrilik asit-g-hidroksipropil akrilat) (PAA-g-PHPA) aşı kopolimerlerinin serbest radikal polimerizasyonu (SRP) yöntemiyle sentezleri gerçekleştirildi. Bunun için ilk aşamada, 2-hidroksietil akrilat (HEA) ve 2-hidroksipropil akrilat (HPA) kullanılarak baz katalizli hidrojen transfer polimerizasyonu (HTP) metoduyla sırasıyla poli(2-hidroksietil akrilat) (PHEA) ve poli(2-hidroksipropil akrilat) (PHPA) elde edildi. Elde edilen bu yapılar zincir uçlarında vinil grupları barındırdığından ikinci aşamada makromonomer olarak kullanıldılar. Bu aşamada “dolaylı aşılama” (“grafting through”) yaklaşımı ile akrilik asit ve bu makromonomerlerin ayrı ayrı serbest radikal polimerizasyonuna (SRP) uğratılmasıyla PAA-g-PHEA ve PAA-g-PHPA aşı kopolimeri elde edildi. Sentezlenen her iki ürünün yapısal ve termal karakterizasyonu en temel spektroskopik ve termal analiz yöntemlerinden olan 1H-NMR, FT-IR ve TGA yöntemleri ile sağlandı. SRP verimlerinin neredeyse %100 olması, nihai ürünlerin 1H-NMR spektrumlarında vinil uç grubuna ait sinyallerin olmaması ve TGA termogramlarında her iki bileşene ait kütle kayıp yüzdesinin neredeyse eşit olması uygulanan sentez stratejisinin başarısını ortaya koymaktadır.

Anahtar Kelimeler

Serbest radikal polimerizasyonu, Hidrojen transfer polimerizasyonu, Aşı kopolimer, “Dolaylı aşılama” stratejisi, Makromonomer

Etik Beyan

Yazarların Katkısı Tüm yazarlar çalışmaya eşit katkıda bulunmuştur. Çıkar Çatışması Beyanı Yazarlar arasında herhangi bir çıkar çatışması bulunmamaktadır. Araştırma ve Yayın Etiği Beyanı Yapılan çalışmada araştırma ve yayın etiğine uyulmuştur.

Kaynakça

• Asan, N., Öztürk, T., Hazer B. (2023). Ters atom transfer radikal polimerizasyon yöntemi ile polietilen glikol ve polimetil metakrilat içeren çok dallı ya da çapraz bağlı kopolimerlerin sentezi ve karakterizasyonu. Karadeniz Fen Bilimleri Dergisi, 13, 1874-1893.
• Beyler Çiğil, A., Şen, F., Birtane, H. Kahraman, M. Z. (2022). Covalently bonded nanosilver-hydroxyethyl cellulose/polyacrylic acid/sorbitol hybrid matrix: thermal, morphological and antibacterial properties. Polymer Bulletin, 79, 11353-11368.
• Cho, H. Y., Krys, P., Szcześniak, K., Schroeder, H., Park, S., Jurga, S., Buback, M., Matyjaszewski, K. (2015). Synthesis of poly(OEOMA) using macromonomers via “grafting-through” ATRP. Macromolecules, 48, 6385-6395.
• Çatıker, E., Güven, O., Salih, B. (2018). Novel hydrophobic macromonomers for potential amphiphilic block copolymers. Polymer Bulletin, 75, 47-60.
• Çatıker, E., Meyvacı, E., Atakay, M., Salih, B., Öztürk, T. (2019). Synthesis and characterization of amphiphilic triblock copolymers including β-alanine/α-methyl-β-alanine and ethylene glycol by “click” chemistry. Polymer Bulletin, 76, 2113-2128.
• Çolakoğlu, G. N., Çatıker, E., Öztürk, T., Meyvacı, E. (2022). Synthesis and characterization of brush-type polyβ-alanine-grafted polymethyl methacrylate using "grafting through" method, Chemical Papers, 76, 869-878.
• Dag, A., Aydin, M., Durmaz, H., Hizal, G., Tunca, U. (2012). Various polycarbonate graft copolymers via Diels-Alder click reaction. Journal of Polymer Science Part A: Polymer Chemistry, 50, 4476-4483.
• Hazer, B., (1992). New macromonomeric initiators (macro-inimers). II. gelation in the bulk polymerization of styrene with macroinimers. Die Makromolekulare Chemie, 193, 1081-1086.
• Hazer, B., Ayas, A., Beşirli, N., Saltek, N., Baysal, B. M. (1989). Preparation of ABCBA-type block copolymers by use of macro-initiators containing peroxy and azo groups. Die Makromolekulare Chemie, 190, 1987-1996.
• Hazer, B., Erdem, B., Lenz, R. W. (1994). Styrene polymerization with some new macro or macromer initiators having PEG units. Journal of Polymer Science Part A: Polymer Chemistry, 32, 1739-1746.
• Iwamura, T., Ashizawa, K., Adachi, K., Takasaki, M. (2019). Anionic hydrogen-transfer polymerization of N-isopropyl acrylamide under microwave irradiation. Journal of Polymer Science Part A: Polymer Chemistry, 57, 2415-2419.
• Macchione, M. A., Biglione, C., Strumia, M. (2018). Design, synthesis and architectures of hybrid nanomaterials for therapy and diagnosis applications. Polymers (Basel), 10, 527.
• Martinez, M. R., Cong, Y., Sheiko, S. S., Matyjaszewski, K. (2020). A thermodynamic roadmap for the grafting-through polymerization of PDMS11MA. ACS Macro Letters, 9, 1303-1309. Öztürk, T., Cavicchi, C. A. (2018). Synthesis and characterization of poly(epichlorohydrin-g-ε-caprolactone) graft copolymers by "click" chemistry. Journal of Polymer Materials, 35, 209-220.
• Neugebauer, D., Zhang, Y., Pakula, T. (2006). Gradient graft copolymers derived from PEO-based macromonomers Journal of Polymer Science Part A: Polymer Chemistry, 44, 1347-1356.
• Öztürk, T., Türkoğlu, H. (2022). Synthesis and characterization of the graft copolymer including polyβ-butyrolactone and polyvinyl chloride by ring-opening polymerization and “click” chemistry. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 59, 871-878.
• Saegusa, T., Kobayashi, S., Kimura, Y. (1975). Hydrogen-transfer polymerization of hydroxyalkyl acrylates. Macromolecules, 8, 950-952.
• Savaş, B., Çatıker, E., Öztürk, T., Meyvacı, E. (2021a). Synthesis and characterization of poly(α-methyl β-alanine)-poly(ε-caprolactone) tri arm star polymer by hydrogen transfer polymerization, ring-opening polymerization and "click" chemistry. Journal of Polymer Research, 28, 30.
• Savaş, B., Çatıker, E., Öztürk, T., Meyvacı, E. (2021b). Synthesis and characterization of poly(methyl methacrylate-g-α-methyl-β-alanine) copolymer using "grafting through" method. Journal of Polymer Research, 28, 194.
• Savaş, B., Çatıker, E., Öztürk, T., Meyvacı, E. (2022). Introduction of 3-hydroxypropionate moieties to polystyrene by “graft through” strategy, ChemistrySelect, 7, e202104193.
• Savaş, B., Öztürk, T. (2020). Synthesis and characterization of poly(vinyl chloride-g-methyl methacrylate) graft copolymer by redox polymerization and Cu catalyzed azide-alkyne cycloaddition reaction. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 57, 819-825.
• Savaş, B., Öztürk, T. (2023). Synthesis and characterization of poly(epichlorohydrin-g-4-vinylbenzyl-g-methyl methacrylate) graft copolymer by combination of ROP, RAFT, and ATRP technics. Journal of Polymer Research, 30, 211.

Synthesis of Novel Macromonomers with Aliphatic Ester-ether Backbone and Their Use in “Grafting Through” Strategy

Yıl 2024, Cilt: 14 Sayı: 3, 1471 – 1485, 15.09.2024

Efkan Çatıker , Temel Öztürk

https://doi.org/10.31466/kfbd.1475630

Öz

In this study, poly(acrylic acid-g-hydroxyethyl acrylate) (PAA-g-PHEA) and poly(acrylic acid-g-hydroxypropyl acrylate) (PAA-g-PHPA) graft copolymers were synthesized by the free-radical polymerization (SRP) method. For this, in the first step, poly(2-hydroxyethyl acrylate) (PHEA) and poly(2-hydroxypropyl acrylate) (PHPA) were obtained by base-catalyzed hydrogen transfer polymerization (HTP) method using 2-hydroxyethyl acrylate (HEA) and 2-hydroxypropyl acrylate (HPA) as monomers, respectively. Since these obtained structures contained vinyl groups at the chain ends, they were used as macromonomers in the second stage. At this stage, PAA-g-PHEA and PAA-g-PHPA graft copolymers were obtained by subjecting acrylic acid and these macromonomers separately to free radical polymerization (SRP) with the “grafting through” approach. Structural and thermal characterization of both synthesized products was achieved by 1H-NMR, FT-IR, and TGA methods, which are among the most basic spectroscopic and thermal analysis methods. The fact that SRP yields are almost 100%, there are no signals of the vinyl end-group in the 1H-NMR spectra of the final products, and the mass loss values of both components are almost equal in the TGA thermograms reveal the success of the applied synthesis strategy.

Anahtar Kelimeler

Free radical polymerization, Hydrogen transfer polymerization, Graft copolymer, “Grafting through” strategy, Macromonomer

Kaynakça

• Asan, N., Öztürk, T., Hazer B. (2023). Ters atom transfer radikal polimerizasyon yöntemi ile polietilen glikol ve polimetil metakrilat içeren çok dallı ya da çapraz bağlı kopolimerlerin sentezi ve karakterizasyonu. Karadeniz Fen Bilimleri Dergisi, 13, 1874-1893.
• Beyler Çiğil, A., Şen, F., Birtane, H. Kahraman, M. Z. (2022). Covalently bonded nanosilver-hydroxyethyl cellulose/polyacrylic acid/sorbitol hybrid matrix: thermal, morphological and antibacterial properties. Polymer Bulletin, 79, 11353-11368.
• Cho, H. Y., Krys, P., Szcześniak, K., Schroeder, H., Park, S., Jurga, S., Buback, M., Matyjaszewski, K. (2015). Synthesis of poly(OEOMA) using macromonomers via “grafting-through” ATRP. Macromolecules, 48, 6385-6395.
• Çatıker, E., Güven, O., Salih, B. (2018). Novel hydrophobic macromonomers for potential amphiphilic block copolymers. Polymer Bulletin, 75, 47-60.
• Çatıker, E., Meyvacı, E., Atakay, M., Salih, B., Öztürk, T. (2019). Synthesis and characterization of amphiphilic triblock copolymers including β-alanine/α-methyl-β-alanine and ethylene glycol by “click” chemistry. Polymer Bulletin, 76, 2113-2128.
• Çolakoğlu, G. N., Çatıker, E., Öztürk, T., Meyvacı, E. (2022). Synthesis and characterization of brush-type polyβ-alanine-grafted polymethyl methacrylate using "grafting through" method, Chemical Papers, 76, 869-878.
• Dag, A., Aydin, M., Durmaz, H., Hizal, G., Tunca, U. (2012). Various polycarbonate graft copolymers via Diels-Alder click reaction. Journal of Polymer Science Part A: Polymer Chemistry, 50, 4476-4483.
• Hazer, B., (1992). New macromonomeric initiators (macro-inimers). II. gelation in the bulk polymerization of styrene with macroinimers. Die Makromolekulare Chemie, 193, 1081-1086.
• Hazer, B., Ayas, A., Beşirli, N., Saltek, N., Baysal, B. M. (1989). Preparation of ABCBA-type block copolymers by use of macro-initiators containing peroxy and azo groups. Die Makromolekulare Chemie, 190, 1987-1996.
• Hazer, B., Erdem, B., Lenz, R. W. (1994). Styrene polymerization with some new macro or macromer initiators having PEG units. Journal of Polymer Science Part A: Polymer Chemistry, 32, 1739-1746.
• Iwamura, T., Ashizawa, K., Adachi, K., Takasaki, M. (2019). Anionic hydrogen-transfer polymerization of N-isopropyl acrylamide under microwave irradiation. Journal of Polymer Science Part A: Polymer Chemistry, 57, 2415-2419.
• Macchione, M. A., Biglione, C., Strumia, M. (2018). Design, synthesis and architectures of hybrid nanomaterials for therapy and diagnosis applications. Polymers (Basel), 10, 527.
• Martinez, M. R., Cong, Y., Sheiko, S. S., Matyjaszewski, K. (2020). A thermodynamic roadmap for the grafting-through polymerization of PDMS11MA. ACS Macro Letters, 9, 1303-1309. Öztürk, T., Cavicchi, C. A. (2018). Synthesis and characterization of poly(epichlorohydrin-g-ε-caprolactone) graft copolymers by "click" chemistry. Journal of Polymer Materials, 35, 209-220.
• Neugebauer, D., Zhang, Y., Pakula, T. (2006). Gradient graft copolymers derived from PEO-based macromonomers Journal of Polymer Science Part A: Polymer Chemistry, 44, 1347-1356.
• Öztürk, T., Türkoğlu, H. (2022). Synthesis and characterization of the graft copolymer including polyβ-butyrolactone and polyvinyl chloride by ring-opening polymerization and “click” chemistry. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 59, 871-878.
• Saegusa, T., Kobayashi, S., Kimura, Y. (1975). Hydrogen-transfer polymerization of hydroxyalkyl acrylates. Macromolecules, 8, 950-952.
• Savaş, B., Çatıker, E., Öztürk, T., Meyvacı, E. (2021a). Synthesis and characterization of poly(α-methyl β-alanine)-poly(ε-caprolactone) tri arm star polymer by hydrogen transfer polymerization, ring-opening polymerization and "click" chemistry. Journal of Polymer Research, 28, 30.
• Savaş, B., Çatıker, E., Öztürk, T., Meyvacı, E. (2021b). Synthesis and characterization of poly(methyl methacrylate-g-α-methyl-β-alanine) copolymer using "grafting through" method. Journal of Polymer Research, 28, 194.
• Savaş, B., Çatıker, E., Öztürk, T., Meyvacı, E. (2022). Introduction of 3-hydroxypropionate moieties to polystyrene by “graft through” strategy, ChemistrySelect, 7, e202104193.
• Savaş, B., Öztürk, T. (2020). Synthesis and characterization of poly(vinyl chloride-g-methyl methacrylate) graft copolymer by redox polymerization and Cu catalyzed azide-alkyne cycloaddition reaction. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 57, 819-825.
• Savaş, B., Öztürk, T. (2023). Synthesis and characterization of poly(epichlorohydrin-g-4-vinylbenzyl-g-methyl methacrylate) graft copolymer by combination of ROP, RAFT, and ATRP technics. Journal of Polymer Research, 30, 211.

Toplam 21 adet kaynakça vardır.

Ayrıntılar

Kaynak Göster

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