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

Abstract

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.

Keywords

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

Project Number

2019.07.06.1021, 2020.07.06.1058

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

Abstract

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.

Keywords

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

Supporting Institution

Düzce Üniversitesi

Project Number

2019.07.06.1021, 2020.07.06.1058

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