Imidazolium‐based poly(ionic liquid)s with poly(ethylene oxide) main chains: Effects of spacer and tail structures on ionic conductivity

Macromol. Rapid Commun.

2018

Self Cite

Glycidyl triazolyl polymer (GTP), which is the product of the Huisgen dipolar cycloaddition reaction between glycidyl azide polymer and alkyne derivatives, is featured here. GTP is the multifunctionalized poly(ethylene glycol) (PEG). The drawback of PEG is that linear PEG has the functional group only at both ends. The low loading capability of the functional groups limits the possibilities of PEG applications. GTP facilitates the synthesis of multifunctionalized PEG derivatives. In this article, 74 examples of GTP homopolymers and copolymers are introduced. The synthetic protocols and work-up processes of GTP are summarized. In addition, application studies are reviewed: for example, stimuli-responsive and self-healing materials, materials for electrical memory devices, ion-conductive materials, and biomedical materials. Finally, some issues on GTP synthesis and future directions for GTP-based polymer materials are proposed.

“…We prepared 24 cationic GTPs as ion‐conductive materials as well ( Figure , Polymers 39 – 62 ) . The ionic conductivity of polyelectrolytes strongly depends on molecular weight.…”

Section: Gtp‐based Functional Polymersmentioning

confidence: 99%

“…Relationship between glass transition temperature and ionic conductivity of cationic GTPs . Equation is depicted by the dotted line.…”

Section: Gtp‐based Functional Polymersmentioning

confidence: 99%

Glycidyl Triazolyl Polymers: Poly(ethylene glycol) Derivatives Functionalized by Azide–Alkyne Cycloaddition Reaction

Macromol. Rapid Commun.

2018

Self Cite

“…However, the study on GTP began to receive much attention in the last 5 years, because GTP is obtainable from readily accessible polyepichlorohydrin . In addition, the application of GTP has been explored in the fields of stimuli‐responsive, self‐healing materials, ion‐conductive materials, and biomedical materials . All of GTPs reported after 2007 were synthesized by Cu(I)‐catalyzed AAC .…”

Section: Introductionmentioning

confidence: 99%

Copper‐Free Synthesis of Glycidyl Triazolyl Polymers

Macro Chemistry & Physics

2018

Self Cite

Five types of glycidyl triazolyl polymers (GTPs) are synthesized without a copper catalyst by thermal azide‐alkyne cycloaddition reaction between glycidyl azide polymer and the electron‐deficient alkynes with the ester group. The samples are characterized by NMR, IR, size‐exclusion chromatography, differential scanning calorimetry, and thermogravimetric analysis. The terminal alkyne affords a 9:1 mixture of the 4‐ and 5‐substituted 1,2,3‐triazolyl derivatives of GTPs. The asymmetric internal alkyne with the methyl‐ and (triethylene glycol)‐esters gives an almost 1:1 mixture of the structural isomers of GTPs having the methyl‐ester substituent at either the 4‐ or 5‐positions of the 1,2,3‐triazole ring. The chemical modification by triethylene glycol improves thermal stability of the ester bond in GTP. The 4,5‐disubstituted triazolyl derivative of GTP has lower glass transition temperature than the mono‐substituted one. This achievement facilitates the work‐up process of GTP synthesis and contributes to expanding the application field of GTP, especially, to the systems not allowing the contamination of a copper catalyst in the biomedical field.

“…Based on this synthetic protocol, we are doing comprehensive study for elucidating the relationship between the molecular design and the ionic conductivity. In our previous study, we characterized the imidazolium‐based poly(ionic liquid)s . Although there are many studies on the imidazolium‐based poly(ionic liquid)s, the report on the other quaternary ammonium cation‐based poly(ionic liquid)s is rare .…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, our polymers have the same degree of polymerization because they were prepared from the same GAP sample by the post‐functionalization method. Therefore, we can discuss the structure‐property relationships unambiguously without influence of molecular weight difference . We determined the order of the cationic units that afford high ionic conductivity.…”

Section: Introductionmentioning

confidence: 99%

Quaternary Ammonium Cation Functionalized Poly(Ionic Liquid)s with Poly(Ethylene Oxide) Main Chains

Macro Chemistry & Physics

Moriyama

Kim

2016

Self Cite

Eight types of cationic glycidyl triazole polymers (GTPs) are prepared from combinations of four quaternary ammonium cationic units (pyrrolidinium, piperidinium, morpholinium, and N,N‐diethyl‐substituted ammonium) and two N‐alkyl substituents (methyl and ethyl groups). These poly(ionic liquid)s are prepared using Cu(I)‐catalyzed azide‐alkyne cycloaddition reaction between the alkyne derivatives of ionic liquids and glycidyl azide polymer. The ionic conductivity is characterized by impedance measurement. The ionic conductivity depends on the type of the cationic unit, but the type of the N‐alkyl substituent shows little influence on the ionic conductivity. The order of the cationic units that afford high ionic conductivity is as follows: pyrrolidinium >N,N‐diethyl‐substituted ammonium > piperidinium > morpholinium. The highest anhydrous ionic conductivity obtained in this study is 9.8 × 10−6 S cm−1 at 30 °C for the GTPs with the 1‐methylpyrrolidinium unit. Based on electrode polarization analysis, the conducting ion (carrier) concentration and mobility are calculated.