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

Macro Chemistry & Physics

2018

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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.

Section: Introductionmentioning

confidence: 99%

Copper‐Free Synthesis of Glycidyl Triazolyl Polymers

Macro Chemistry & Physics

2018

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“…Although ionic liquids are well-known as designer solvents, the implementation of a new design on poly(ionic liquid)s is often difficult because more complicated monomer design makes the polymerization more difficult. Because the ionic conductivity strongly depends on the molecular weight, it is difficult to judge whether high ionic conductivity originates from good molecular design or low molecular weight in the case of poly(ionic liquid)s with the molecular weight of <10 5 g mol –1 . − In order to solve this issue, high-molecular-weight poly(ionic liquid)s ( M w > 10 6 g mol –1 ) have been developed based on cationic glycidyl triazolyl polymers (cationic GTPs). − Cationic GTPs were synthesized by postfunctionalization via a Cu(I)-catalyzed azide–alkyne cycloaddition (Cu-AAC) between the glycidyl azide polymer (GAP) and alkyne derivatives of ionic liquids . The post functionalization enables the implementation of complicated molecular design on poly(ionic liquid)s.…”

mentioning

confidence: 99%

“…In order to discuss the ionic conductivity data in more detail, the impedance data were analyzed by the electrode polarization (EP) model. , The values of the conducting ion concentration ( p , cm –3 ), conducting ion mobility (μ, cm 2 V –1 s –1 ), and static dielectric constant (ε s ) were calculated and summarized in Tables S4–S6. − ,, The conducting ion concentration ( p ) of PEO- co -GTP·3FSI was slightly higher than that of PEO- co -GTP·3TFSI (Table ). Assuming a copolymer density of 1.4 g cm –3 , the counterion concentrations of PEO- co -GTP·3TFSI and PEO- co -GTP·3FSI were calculated to be 1.4 × 10 21 and 1.7 × 10 21 cm –3 , respectively.…”

mentioning

confidence: 99%

Poly(ionic liquid)s Based on Copolymers of Poly(ethylene oxide) and Cationic Glycidyl Triazolyl Polymers with Tribranched Side Chains

2021

ACS Macro Lett.

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Copolymers comprising poly(ethylene oxide) and cationic glycidyl triazolyl polymer with tribranched side chains (PEO-co-GTP·3X) were synthesized from glycidyl azide copolymer (PEO-co-GAP) and the tricationic alkyne. A synthetic route for the tricationic alkyne was also improved. Bis(trifluoromethanesulfonyl)imide (TFSI) and bis(fluorosulfonyl)imide (FSI) were used as counteranions. Copolymers PEO-co-GTP·3TFSI and PEO-co-GTP·3FSI were characterized by NMR, IR, size exclusion chromatography, DSC, TGA, rheological, and impedance measurements. The NMR results suggested that the main chain of the copolymer was more flexible than that of the homopolymer. However, no major changes were detected in the glass transition temperature and ionic conductivity of the homopolymer and copolymer with TFSI counteranions. The counterion exchange from TFSI to FSI resulted in an increase in the storage modulus and complex viscosity because of the ionic association. Despite its unfavorable viscoelastic properties, PEO-co-GTP·3FSI exhibited higher ionic conductivity than PEO-co-GTP·3TFSI (3.9 × 10–5 S cm–1 at 25 °C under anhydrous conditions).

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

Macromol. Rapid Commun.

2018

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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.