Alternating Copolymerization Realized with Alternating Transformation of Anion-Migrated Ring-Opening Polymerization and Anionic Polymerization Mechanisms

2021 ◽  
Author(s):  
Hongyuan Bai ◽  
Li Han ◽  
Chao Li ◽  
Songbo Zhang ◽  
Xuefei Wang ◽  
...  
Keyword(s):  
Anionic Polymerization ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Alternating Copolymerization

scholarly journals Anionic Polymerization of β-Butyrolactone Initiated with Sodium Phenoxides. The Effect of the Initiator Basicity/Nucleophilicity on the ROP Mechanism

Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1221 ◽  
Author(s):  
Adrian Domiński ◽  
Tomasz Konieczny ◽  
Magdalena Zięba ◽  
Magdalena Klim ◽  
Piotr Kurcok
Keyword(s):  
Anionic Polymerization ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Elimination Reaction ◽  
Mild Conditions ◽  
Acidic Proton ◽  
End Groups ◽  
Anionic Ring

It was shown that selected sodium phenoxide derivatives with different basicity and nucleophilicity, such as sodium p-nitrophenoxide, p-chlorophenoxide, 1-napthoxide, phenoxide and p-methoxyphenoxide, are effective initiators in anionic ring-opening polymerization (AROP) of β-butyrolactone in mild conditions. It was found that phenoxides as initiators in anionic ring-opening polymerization of β-butyrolactone behave as strong nucleophiles, or weak nucleophiles, as well as Brønsted bases. The resulting polyesters possessing hydroxy, phenoxy and crotonate initial groups are formed respectively by the attack of phenoxide anion at (i) C2 followed by an elimination reaction with hydroxide formation, (ii) C4 and (iii) abstraction of acidic proton at C3. The obtained poly(3-hydroxybutyrate) possesses carboxylate growing species. The ratio of the observed initial groups strongly depends on the basicity and nucleophilicity of the sodium phenoxide derivative used as initiator. The proposed mechanism of this polymerization describes the reactions leading to formation of observed end groups. Moreover, the possibility of formation of a crotonate group during the propagation step of this polymerization is also discussed.

scholarly journals Synthesis and anionic polymerization of isosorbide mono-epoxides for linear biobased polyethers

2021 ◽  
Author(s):  
Livia Matt ◽  
Ilme Liblikas ◽  
Olivier Bonjour ◽  
Patric Jannasch ◽  
Lauri Vares
Keyword(s):  
Anionic Polymerization ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Anionic Ring

A series of regioisomeric isosorbide mono-epoxides, as well as diastereomerically pure mono-epoxy derivatives, have been prepared and studied. Anionic ring-opening polymerization of methoxy-capped monomers produced linear polyethers tethered with isosorbide...

Anionic Ring Opening Polymerization of ε-Caprolactone Initiated by Lithium Silanolates

2017 ◽  
Vol 70 (1) ◽  
pp. 106 ◽  
Author(s):  
Angel J. Satti ◽  
Augusto G. O. de Freitas ◽  
M. Loreta Sena Marani ◽  
Marcelo A. Villar ◽  
Enrique M. Vallés ◽  
...  
Keyword(s):  
Anionic Polymerization ◽  
Ring Opening ◽  
High Vacuum ◽  
Ring Opening Polymerization ◽  
Anionic Ring

Ring-opening homo- and co-polymerization reactions of ϵ-caprolactone were performed by employing anionic polymerization (high vacuum techniques) and lithium silanolates (LS) as initiators. LS were obtained by reaction between hexamethyl(cyclotrisiloxane) and sec-Bu–Li+, or from living poly(dimethylsiloxanyl)lithium chains. The results indicated that LS are efficient initiators for the ring-opening polymerization of ϵ-caprolactone, providing the respective homogeneous polymers in good yields.

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