Synthesis of Linear, Cyclic, Figure-Eight-Shaped, and Tadpole-Shaped Amphiphilic Block Copolyethers via t-Bu-P4-Catalyzed Ring-Opening Polymerization of Hydrophilic and Hydrophobic Glycidyl Ethers

2014 ◽  
Vol 47 (9) ◽  
pp. 2853-2863 ◽  
Author(s):  
Takuya Isono ◽  
Yusuke Satoh ◽  
Kana Miyachi ◽  
Yougen Chen ◽  
Shin-ichiro Sato ◽  
...  
2019 ◽  
Vol 26 (12) ◽  
Author(s):  
Zbigniew Grobelny ◽  
Justyna Jurek-Suliga ◽  
Sylwia Golba

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.


2016 ◽  
Vol 49 (2) ◽  
pp. 499-509 ◽  
Author(s):  
Yusuke Satoh ◽  
Kana Miyachi ◽  
Hirohiko Matsuno ◽  
Takuya Isono ◽  
Kenji Tajima ◽  
...  

Polymers ◽  
2021 ◽  
Vol 13 (13) ◽  
pp. 2150
Author(s):  
Justyna Jurek-Suliga ◽  
Zbigniew Grobelny ◽  
Sylwia Golba ◽  
Hubert Okła ◽  
Katarzyna Bednarczyk

Polyether-pentols (PEPOs) were synthesized from glycidyl ethers and butylene oxide with the application of tripotassium salts of 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol (HMCH) activated 18C6 for ring-opening polymerization (ROP). The construction of the applied initiator system reflects the ability of crown ether to influence the degree of ion-pair separation with an increased activating effect. As a result formation of bi- or trimodal polymers was observed with molar masses in the range of (Mn = 1200–6000). The observed multi-fraction composition is prescribed to the formation of ionic aggregates with different reactivities during polymerization. The mechanism of the studied processes is discussed. The obtained PEPOs served for a crosslinked PUR synthesis, for which the hydrogen bond index for coupling of hard segments was calculated. Additionally, the range of phase separation was calculated that was higher for PUR-containing aromatic rings as the substituent.


2020 ◽  
Author(s):  
Nathaniel Park ◽  
Dmitry Yu. Zubarev ◽  
James L. Hedrick ◽  
Vivien Kiyek ◽  
Christiaan Corbet ◽  
...  

The convergence of artificial intelligence and machine learning with material science holds significant promise to rapidly accelerate development timelines of new high-performance polymeric materials. Within this context, we report an inverse design strategy for polycarbonate and polyester discovery based on a recommendation system that proposes polymerization experiments that are likely to produce materials with targeted properties. Following recommendations of the system driven by the historical ring-opening polymerization results, we carried out experiments targeting specific ranges of monomer conversion and dispersity of the polymers obtained from cyclic lactones and carbonates. The results of the experiments were in close agreement with the recommendation targets with few false negatives or positives obtained for each class.<br>


2019 ◽  
Vol 52 (23) ◽  
pp. 9232-9237 ◽  
Author(s):  
Rukshika S. Hewawasam ◽  
U. L. D. Inush Kalana ◽  
Nayanthara U. Dharmaratne ◽  
Thomas J. Wright ◽  
Timothy J. Bannin ◽  
...  

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