Synthesis of Well-Defined Amphiphilic Star-Block and Miktoarm Star Copolyethers via t-Bu-P4-Catalyzed Ring-Opening Polymerization of Glycidyl Ethers

2016 ◽  
Vol 49 (2) ◽  
pp. 499-509 ◽  
Author(s):  
Yusuke Satoh ◽  
Kana Miyachi ◽  
Hirohiko Matsuno ◽  
Takuya Isono ◽  
Kenji Tajima ◽  
...  
Keyword(s):  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Glycidyl Ethers ◽  
Miktoarm Star

scholarly journals Ring-opening polymerization of monosubstituted oxiranes in the presence of potassium hydride: determination of initiation course and structure of macromolecules by MALDI-TOF mass spectrometry

2019 ◽  
Vol 26 (12) ◽  
Author(s):  
Zbigniew Grobelny ◽  
Justyna Jurek-Suliga ◽  
Sylwia Golba
Keyword(s):  
Mass Spectrometry ◽  
Ring Opening ◽  
Glycidyl Ether ◽  
Ring Opening Polymerization ◽  
Size Exclusion ◽  
Oxirane Ring ◽  
Maldi Tof ◽  
Glycidyl Ethers ◽  
Initiation Step ◽  
Potassium Hydride

AbstractSeveral monosubstituted oxiranes were polymerized with suspension of potassium hydride (KH) in tetrahydrofuran (THF) at room temperature. This heterogeneous process resulted in polyethers with various starting groups depending on the kind of monomer. The macromolecules formed in ring-opening polymerization of monosubstituted oxiranes were analyzed by Matrix Assisted Laser Desorption/Ionization - Time of Flight Mass Spectrometry (MALDI-TOF MS). It was stated, that initiation of propylene oxide (PO) polymerization with KH proceeded via three ways, i.e. cleavage of oxirane ring in the β-position, monomer deprotonation and deoxygenation. Potassium isopropoxide, potassium allyloxide and potassium hydroxide were the real initiators. The main reactions, which occur in the initiation step, depend on the type of monomer used. In the case of allyl glycidyl ether (AGE) and phenyl glycidyl ether (PGE) deprotonation of the monomer did not occur. During initiation of glycidyl ethers oxirane ring was opened and also linear ether bond between glycidyl group and oxygen atom was cleaved under influence of KH. Interestingly, formation of new kinds of macromolecules was observed in the systems containing glycidyl ethers, which do not possess mers of the monomers used. Mechanisms of the studied processes were presented and discussed. Carbon-13 Nuclear Magnetic Resonance (13C NMR) was used as supporting technique for analysis of the obtained polymers. Number average molar masses of the polymers (Mn) determined by Size Exclusion Chromatography (SEC) were about two times higher than calculated ones. It indicated that half of used KH did not take part in the initiation step.

Synthesis of miktoarm star-shaped and inverse star-block copolymers by a combination of ring-opening polymerization and click chemistry

e-Polymers ◽  
2018 ◽  
Vol 18 (6) ◽  
pp. 559-568 ◽  
Author(s):  
Xiaoqi Yan ◽  
Jianbo Li ◽  
Tianbin Ren
Keyword(s):  
Block Copolymer ◽  
Ring Opening ◽  
Click Reaction ◽  
Ring Opening Polymerization ◽  
Structure And Properties ◽  
Star Block Copolymer ◽  
Ft Ir ◽  
Miktoarm Star ◽  
Star Block Copolymers ◽  
Ft Ir Spectroscopy

AbstractBased on the combination of the “arm-first” and “core-first” strategies, the miktoarm star-shaped copolymer PLLA2PCL2 and the inverse star-block copolymer (PCL-b-PLLA)2-core-(PCL-b-PLLA)2 were designed and synthesized by the combination of ring-opening polymerization (ROP) and a click reaction. The miktoarm star-shaped copolymer PLLA2PCL2 was synthesized by a click reaction of an azido macroinitiator PLLA2(N3)2 and HC≡C-PCL. The inverse star-block copolymer (PCL-b-PLLA)2-core-(PCL-b-PLLA)2 was synthesized by a click reaction of an azido macroinitiator (PCL-b-PLLA)2(N3)2 and HC≡C-PCL-b-PLLA. The structures of these star polymers were confirmed by nuclear magnetic resonance (NMR), Fourier-transform infrared (FT-IR) spectroscopy and gel permeation chromatograph (GPC). The inverse star-block copolymer could be used to study the potential relationship between polymer structure and properties, which has a unique structure and good crystallization properties.

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