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[Taichi Ikeda](https://orcid.org/0000-0001-6650-5798)

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[Copper‐Free Synthesis of Cationic Glycidyl Triazolyl Polymers](https://mdr.nims.go.jp/datasets/a5711162-3586-4198-a8bb-e810a4c0ad97)

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Copper‐Free Synthesis of Cationic Glycidyl Triazolyl PolymersRESEARCH ARTICLEwww.mrc-journal.deCopper-Free Synthesis of Cationic Glycidyl TriazolylPolymersTaichi IkedaCopper-free synthesis of cationic glycidyl triazolyl polymers (GTPs) is achievedthrough a thermal azide-alkyne cycloaddition reaction between glycidyl azidepolymer and propiolic acid, followed by decarboxylation and quaternization ofthe triazole unit. For synthesizing nonfunctionalized GTP (GTP-H), amicrowave-assisted method enhances the decarboxylation reaction ofcarboxy-functionalized GTP (GTP-COOH). Three variants of cationic GTPswith different N-substituents [N-ethyl, N-butyl, and N-tri(ethylene glycol)monomethyl ether (EG3)] are synthesized. The molecular weight of GTP-H isdetermined via size exclusion chromatography. Thermal properties of all GTPsare characterized using differential scanning calorimetry andthermogravimetric analysis. The ionic conductivities of these cationic GTPsare assessed by impedance measurements. The conducting ion concentrationand mobility are calculated based on the electrode polarization model. Amongthree cationic GTPs, the GTP with the N-EG3 substituent exhibits the highestionic conductivity, reaching 6.8 × 10−6 S cm−1 at 25 °C under dry conditions.When compared to previously reported reference polymers, the reduction ofsteric crowding around the triazolium unit is considered to be a key factor inenhancing ionic conductivity.1. IntroductionPolymer electrolytes based on poly(ionic liquid)s are valuablematerials across a range of applications, including batteries,[1,2]fuel cells,[3,4] supercapacitors,[5–7] solar cells,[8,9] electrochromicdevices,[10,11] actuators,[12,13] CO2 absorption,[14,15] and separationmembranes,[16,17] owing to their excellent processability and highdesign flexibility. While most research groups have focused ondeveloping acrylate polymer-based poly(ionic liquid)s throughthe polymerization of ionic liquid monomers,[18–21] our group hasexplored poly(ionic liquid)s based on glycidyl triazolyl polymers(GTPs).[22–27] These GTPs are synthesized via a Cu(I)-catalyzedT. Ikeda1-1 NamikiTsukuba, Ibaraki 305-0044, JapanE-mail: ikeda.taichi@nims.go.jpThe ORCID identification number(s) for the author(s) of this articlecan be found under https://doi.org/10.1002/marc.202400416© 2024 The Author(s). Macromolecular Rapid Communicationspublished by Wiley-VCH GmbH. This is an open access article under theterms of the Creative Commons Attribution License, which permits use,distribution and reproduction in any medium, provided the original workis properly cited.DOI: 10.1002/marc.202400416azide-alkyne cycloaddition reaction be-tween glycidyl azide polymer (GAP) andcationic or anionic alkyne derivatives.A significant advantage of our GTP-based poly(ionic liquid)s is their post-functionalization capability, allowing forthe preparation of a series with consistentdegrees of polymerization to elucidate thestructure–property relationships.[22,27,28]However, the use of the copper catalystrequires a tedious and time-consumingwork-up procedure for purification. Toaddress this issue, a new synthetic routefor GTP-based poly(ionic liquid)s with-out a copper catalyst has been developedin this study, which involves: i) thermalazide-alkyne cycloaddition between GAPand propiolic acid to produce carboxy-functionalized GTP (GTP-COOH), ii)synthesis of nonfunctionalized GTP (GTP-H) through decarboxylation of GTP-COOH,and iii) synthesis of cationic GTP throughquaternization of the triazole group. Thesefirst two steps were originally reported byH. L. Cohen in 1981.[29] Although Cohenmentioned the synthesis of GTP-H as an example of the chemi-cal modification of various azide polymers, the details of the syn-thetic procedure and characterization results were not reportedbeyond CHN elemental analysis data. There is no further chem-ical and physical data on GTP-H because nobody revisited hisachievement since 1981. In this study, we have successfully repli-cated Cohen’s methodology and refined the synthetic procedure,particularly finding that microwave-assisted reaction efficientlypromotes the decarboxylation of GTP-COOH.In this study, three types of cationic GTPs with different N-substitutions [-ethyl, butyl, and tri(ethylene glycol) monomethylether] (Figure 1a–c) were synthesized, and their thermal proper-ties and ionic conductivity were characterized. The triazolium-based poly(ionic liquid)s have been extensively reported.[30–36]Among these, GTP-(N-Me)-EG3·TFSI (Figure 1d) served as areference polymer, synthesized through a copper(I)-catalyzedazide-alkyne cycloaddition.[36] In addition, imidazolium-basedpoly(ionic liquid) with a glycidyl main chain (GP-Im-Bu·TFSI)was also selected as a reference polymer for comparison(Figure 1e).[37] It was found that GTP-N-Bu·TFSI exhibitedionic conductivity comparable to GP-Im-Bu·TFSI, while GTP-N-EG3·TFSI showed higher ionic conductivity than GTP-(N-Me)-EG3·TFSI. The influence of the substituents on the triazole uniton ionic conductivity is discussed in this study.Macromol. Rapid Commun. 2024, 45, 2400416 2400416 (1 of 7) © 2024 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbHhttp://www.mrc-journal.demailto:ikeda.taichi@nims.go.jphttps://doi.org/10.1002/marc.202400416http://creativecommons.org/licenses/by/4.0/http://crossmark.crossref.org/dialog/?doi=10.1002%2Fmarc.202400416&domain=pdf&date_stamp=2024-07-02www.advancedsciencenews.com www.mrc-journal.deFigure 1. a–c) Chemical structures of cationic GTPs in this study, and d,e)reference polymers in previous studies.2. Results and Discussion2.1. Synthesis of Cationic GTPsThe synthetic route of GTP-H is illustrated in Scheme 1.Polyepichlorohydrin (PECH) was reacted with sodium azide(NaN3) in DMF at 90 °C for 24 h. This reaction condition led to100% conversion from PECH to GAP.[22–27] In our previous stud-ies, GAP was precipitated by gradually adding the reaction solu-tion to water.[22–27] However, for safety reasons, it is preferable toproceed to the next reaction without isolating GAP in solid form,due to its high-energy content and associated explosion risk.[38]H. L. Cohen demonstrated that subsequent reactions could beconducted directly after removing the salts (NaCl and unreactedNaN3) from the solution by filtration. It was confirmed that thisapproach was effective, yielding a white product after reactingwith propiolic acid in DMF at 50 °C for 3 d. The quantitative con-version from GAP to GTP-COOH was confirmed by the disap-pearance of the azide peak (𝜈 = 2100 cm−1) in the IR spectrum.While higher reaction temperature reduced the reaction time, italso caused significant discoloration of the solution.H. L. Cohen performed the decarboxylation of GTP-COOHat 190 °C in N-methylpyrrolidone (NMP) for 4 h.[29] We foundthat decarboxylation could be conducted at a lower temperature(150 °C) using N,N-dimethylformamide (DMF), which is morecost effective and easier to evaporate than NMP, making this apreferable reaction condition. Figure 2 displays the conversionFigure 2. Conversion versus time plot for the decarboxylation reaction ofGTP-COOH. The reaction was conducted in a DMF solution, with the re-action time starting upon reaching 150 °C.Scheme 2. Synthesis of cationic GTPs.versus time curves for the decarboxylation reaction, determinedfrom the integrals of the triazole peak in the 1H NMR spectrum(Figure S10, Supporting Information). Using an aluminum reac-tion/heating block at 150 °C, the reaction took eight hours to com-plete. A microwave-assisted reaction dramatically shortened thistime to one hour (Figure 2). The acceleration of the decarboxy-lation reaction by the microwave irradiation has been reportedby some groups.[39–41] It was hypothesized that the microwave ef-fects would arise from large polarity change between the groundstate and the transition state in the decarboxylation reaction.[41,42]The quaternization of the triazole group was carried outby reacting with iodide compounds (Scheme 2). The reactionconditions are summarized in Table 1. Following the counte-rion metathesis with lithium bis(trifluoromethanesulfonyl)imide(Li·TFSI), the cationic GTPs were obtained. For the N-ethyl andN-butyl variants, transparent pale-yellow rubbers were produced.The synthesis of GTP-N-EG3·TFSI required higher temperaturesand longer reaction times, resulting in a transparent orange rub-ber. Although the conversion of triazole to triazolium groups wasScheme 1. Synthetic route of non-functionalized GTP.Macromol. Rapid Commun. 2024, 45, 2400416 2400416 (2 of 7) © 2024 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2024, 24, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202400416 by National Institute For, Wiley Online Library on [09/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.dewww.advancedsciencenews.com www.mrc-journal.deTable 1. Reaction conditions and yields of cationic GTPs.GTP R Ta) [°C] tb) [h] Yield [%]GTP-N-Et·TFSI C2H5 70 24 75GTP-N-Bu·TFSI C4H9 80 24 73GTP-N-EG3·TFSI (C2H4O)3CH3 100 48 68a)Reaction temperature;b)Reaction time.complete (100%), the yield was ≈70% due to losses during theprecipitation purification process (Table 1).The chemical structures of the products were confirmed us-ing 1H, 13C, and 2D NMR spectroscopy. Figure 3a presents the1H NMR spectra of GTP-COOH, where thermal azide-alkynecycloaddition results in a mixture of 4- and 5-functionalizedtriazoles.[43] The peaks at 8.58 and 8.00 ppm correspond to the tri-azole protons of 4- and 5-functionalized products, respectively,[43]with a ratio of 9:1 determined from the integrals of these peaks.The integrals of 1H NMR peaks are shown in Figures S1–S5(Supporting Information). The disappearance of water and car-boxyl proton peaks is likely due to the intermediate exchangerate via hydrogen bonding on the NMR timescale. Figure 3billustrates the 1H NMR spectra of GTP-H. Peak assignmentswere facilitated by 1H-13C heteronuclear multiple bond coher-ence (HMBC) spectroscopy, which indicated a cross-peak be-tween proton c and carbon d (Figure S7, Supporting Informa-tion). The glycidyl protons (a, b, and c) in GTP-H appear simplercompared to those in GTP-COOH, due to the absence of struc-tural isomer. Figure 3c displays the 13C NMR spectra of GTP-N-Et·TFSI, confirming the presence of glycidyl (a, b, and c), tria-zolium (d and e), ethyl group (f and g), and TFSI counter anioncarbons. The HMBC spectra showed cross-peaks between protonc and carbon d, and between proton f and carbon e (Figure S9,Supporting Information). The carbon of the CF3 group split intoa quartet due to 13C–19F spin–spin coupling.[44] Comparing GTP-N-EG3·TFSI with the reference polymer GTP-(N-Me)-EG3·TFSI(Figure 1d), the triazolium proton peak of GTP-(N-Me)-EG3·TFSI(d) is broader than those of GTP-N-EG3·TFSI (d and e, FigureS11, Supporting Information).[36] This broadening is likely dueto the different steric environments surrounding the triazoliumunits in GTP-N-EG3·TFSI and GTP-(N-Me)-EG3·TFSI. The tria-zolium unit in GTP-(N-Me)-EG3·TFSI has two substituents at the3- and 4-positions, whereas GTP-N-EG3·TFSI has only one sub-stituent at the 3-position. The presence of additional substituentsin GTP significantly impacts the dynamics of the triazolium unitdue to its proximity to the main chain, leading to peak broaden-ing from restricted dynamics with short NMR relaxation time.[22]The molecular weight of GTP-H was determined by size ex-clusion chromatography (SEC), using polystyrene as a standard.Figure S12 (Supporting Information) presents the SEC chartFigure 3. 1H NMR spectra of a) GTP-COOH and b) GTP-H (DMSO-d6, 400 MHz); c) 13C NMR spectra of GTP-N-Et·TFSI (CD3CN, 100 MHz).Macromol. Rapid Commun. 2024, 45, 2400416 2400416 (3 of 7) © 2024 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2024, 24, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202400416 by National Institute For, Wiley Online Library on [09/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.dewww.advancedsciencenews.com www.mrc-journal.deTable 2. Molecular weight and thermal properties of GTPs.GTP Mna)[g mol−1]Mwb)[g mol−1]Tgc)[°C]Td5d)[°C]GTP-COOHe) 2.2 × 105f) 3.4 × 105g) 110.6 173GTP-Hh) 1.6 × 105 2.5 × 105 47.5 337GTP-N-Et·TFSI 5.6 × 105f) 8.8 × 105g) −11.3 350GTP-N-Bu·TFSI 5.9 × 105f) 9.4 × 105g) −14.6 340GTP-N-EG3·TFSI 7.1 × 105f) 1.1 × 106g) −24.3 325a)Number-average molecular weight;b)Weight-average molecular weight;c)Glasstransition temperature, onset value of DSC curve;d)5 wt% decomposition temper-ature determined by TGA curve;e)Mixture of 4-functionalized and 5-functionalizedtriazoles;f)Calculated value based on number-average degree of polymerization ofGTP-H;g)Calculated value based on weight-average degree of polymerization ofGTP-H;h)Polydispersity index PDI = 1.6.for GTP-H. The number-average and weight-average molecularweights (Mn and Mw) were 1.6 × 105 and 2.5 × 105 g mol−1, re-spectively. Attempts to measure the molecular weights of GTP-COOH and cationic GTPs by SEC were unsuccessful, as no peaksappeared on the SEC chart, likely due to adsorption onto the col-umn resin. Table 2 summarizes the Mn and Mw values of theGTPs, calculated based on the number- and weight-average de-grees of polymerization of GTP-H.2.2. Thermal PropertiesThermal properties were characterized using differential scan-ning calorimetry (DSC) and thermogravimetric analysis (TGA).Figure 4 displays the DSC charts for all GTPs, which exhib-ited glass transitions without melting or crystallization peaks.The glass transition temperatures (Tg) are detailed in Table 2.The main product of GTP-COOH in this study is the 4-functionalized product, although GTP-COOH is a mixture withthe 5-functionalized variant. Consequently, the Tg of GTP-COOHin this study (110.6 °C) is comparable to the previously re-Figure 4. a–e) DSC charts of GTP-COOH, GTP-H, GTP-N-Et·TFSI, GTP-N-Bu·TFSI, and GTP-N-EG3·TFSI. Heating rate: 10 °C min−1.Figure 5. a–e) TGA charts of GTP-COOH, GTP-H, GTP-N-Et·TFSI, GTP-N-Bu·TFSI, and GTP-N-EG3·TFSI. Heating rates were set at 5 °C min−1 forGTP-COOH and 10 °C min−1 for the others.ported value for GTP-COOH synthesized with a Cu(I) catalyst(110.8 °C);[45] however, the step change at Tg in Figure 4a wasless pronounced than previously reported. The Tg of GTP-H wasslightly above room temperature at 47.5 °C, and the Tgs of thecationic GTPs were below room temperature, rendering thesepolymers as adhesive rubber materials. It was confirmed that alonger N-substituent resulted in a lower Tg value.Figure 5 illustrates the TGA charts. The 5 wt% loss tem-peratures (Td5s) are summarized in Table 2. For GTP-COOH(Figure 5a), a 26 wt% weight loss was observed between 150 and220 °C, consistent with the expected weight loss from the decar-boxylation reaction (monomer unit molecular weights of GTP-COOH and GTP-H are 169.14 and 125.13 g mol−1, respectively).The second significant weight loss for GTP-COOH occurred atthe same temperature as the thermal decomposition of GTP-H(Figure 5b), as these are composed of the same polymer base.The Td5 values of the cationic GTPs were above 300 °C, indicat-ing their thermal stability.2.3. Ionic ConductivityThe ionic conductivity of the cationic GTPs was determined us-ing impedance spectroscopy under dry conditions.[46] The directcurrent conductivity (𝜎DC) was derived from the plateau regionof the conductivity versus frequency plot (Figure S13, SupportingInformation). The temperature dependence of the ionic conduc-tivity for the cationic GTPs followed a Vogel–Fulcher–Tammann(VFT)-type behavior (Figure 6), indicating that ionic conductionis linked to the segmental motion of the polymer chains.[22–27]The data were analyzed using the equation𝜎DC = 𝜎0 × exp{−B∕(T − T0)}(1)where 𝜎0, B, and T0 are constants.[22] The parameters obtainedfrom the fit are summarized in Table 3.Macromol. Rapid Commun. 2024, 45, 2400416 2400416 (4 of 7) © 2024 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2024, 24, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202400416 by National Institute For, Wiley Online Library on [09/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.dewww.advancedsciencenews.com www.mrc-journal.deFigure 6. Temperature dependence of DC conductivity (𝜎DC). Dashedcurves represent fits using Equation (1). Fitting parameters are providedin Table 3.The 𝜎DC values at 25 °C for the cationic GTPs were approxi-mately 10−6 S cm−1. GTP-N-EG3·TFSI exhibited the highest ionicconductivity across all temperatures. This superior performanceis likely due to its lowest Tg among the cationic GTPs. Using thefitting parameters and Equation (1), the 𝜎DC value for GTP-N-EG3·TFSI at 30 °C was calculated to be 1.2 × 10−5 S cm−1, higherthan that of the reference polymer GTP-(N-Me)-EG3·TFSI (7.5 ×10−6 S cm−1).[36] Taking the fact that GTP-N-EG3·TFSI has higherTg value (−24.2 °C) than GTP-(N-Me)-EG3·TFSI (−37 °C) intoaccount,[36] this result looks to be strange, because the poly(ionicliquid)s with lower Tg usually exhibit higher ionic conductivity.Lower Tg value of GTP-(N-Me)-EG3·TFSI than GTP-N-EG3·TFSIcan be explained by the previously reported experimental resultsthat the increasing the number of the side groups often decreasesTg value due to the shielding of interactions between the poly-mer main chains.[22,43] As discussed above with the NMR results,the sterically crowded environment around the triazolium unit inGTP-(N-Me)-EG3·TFSI lowers the dynamics of the cationic unit.Presumably, the dynamics of the cationic unit might be more im-portant to promote the ion conduction than the segmental dy-namics of the other parts which determine the Tg value.Conversely, the 𝜎DC value for GTP-N-Bu·TFSI at 30 °C (5.0× 10−6 S cm−1) was comparable to that of the reference poly-mer GP-Im-Bu·TFSI (5.3 × 10−6 S cm−1 at 30 °C),[37] reflectingsimilar steric structures which may influence ionic conductiv-ity. The Tg values of GTP-N-Bu·TFSI and GP-Im-Bu·TFSI wereTable 3. Ionic conductivity of cationic GTPs and fitting parameters forEquation (1).GTP 𝜎DC (25 °C)[S cm−1]𝜎0 [S cm−1] B T0 [K]GTP-N-Et·TFSI 2.1 × 10−6 0.1233 778.2 226.8GTP-N-Bu·TFSI 2.6 × 10−6 0.1467 933.8 212.4GTP-N-EG3·TFSI 6.8 × 10−6 0.0791 729.0 219.8Figure 7. Temperature dependency of a) conducting ion concentration (p)and b) conducting ion mobility (μ) values.also comparable (−14.6 and −12 °C, respectively).[37] Comparedto cationic GTPs with different alkyl substituents (N-ethyl andN-butyl), GTP-N-Et·TFSI showed a stronger temperature depen-dency than GTP-N-Bu·TFSI. At higher temperatures, the ionicconductivity of GTP-N-Et·TFSI exceeds that of GTP-N-Bu·TFSI,despite its higher Tg.For further analysis, the 𝜎DC value was decomposed into twocomponents: the conducting ion concentration (p) and the con-ducting ion mobility (μ), using the electrode polarization model(Supporting Information).[47–49] The 𝜎DC value is expressed as theproduct of the elemental charge (1.60 × 10−19 C), p, and μ values[Equation (2)].𝜎DC = e ⋅ p ⋅ 𝜇 (2)Figure 7 illustrates the temperature dependence of the con-ducting ion concentration (p) and mobility (μ) values. The p val-ues for all cationic GTPs were in the order of 1016 cm−3, which arerelatively smaller compared to the previously reported cationicGTPs with p-values on the order of 1017 cm−3.[22,25,26] This differ-ence is attributed to the positioning of the cationic unit; in thisstudy, the cationic unit is located near the main chain, whereasin previous studies, it was at the end of side chains. Colby et al.reported that poly(ionic liquid)s with a long spacer between themain chain and the cationic unit exhibited higher conducting ionconcentrations than those with an intermediate-length spacer.[50]The N-EG3 substituent demonstrated a higher p-value comparedto the N-alkyl substituents (Figure 7a), likely because the ethy-lene glycol chains enhance ion-pair dissociation.[20,21,51] In addi-Macromol. Rapid Commun. 2024, 45, 2400416 2400416 (5 of 7) © 2024 The Author(s). Macromolecular Rapid Communications published by Wiley-VCH GmbH 15213927, 2024, 24, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/marc.202400416 by National Institute For, Wiley Online Library on [09/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.dewww.advancedsciencenews.com www.mrc-journal.detion, the long, flexible ethylene glycol side chains soften the poly-mer matrix and facilitate ion diffusion, leading to a higher μ valuethan those of the N-alkyl substituents (Figure 7b). From these p-and μ-values, it is evident that the different temperature depen-dencies of the 𝜎DC value between the N-ethyl and N-butyl sub-stituents arise from the μ value’s temperature dependency. Simi-lar trends have been observed in other polymers, such as the dy-namics of poly(alkyl methacrylate)s,[52] diffusion of CH4 and CO2molecules in the poly(alkyl acrylate) matrix,[53] and the ionic con-ductivity of poly(ionic liquid)s.[54] The shorter side chains provideless shielding of interactions between the polymer main chains,leading to a more significant decrease in polymer chain dynamicswith temperature compared to longer side chains.3. ConclusionCationic GTPs have been successfully synthesized through athermal azide-alkyne synthesis followed by decarboxylation andquaternization of the triazole unit. This research revisited theachievements of H. L. Cohen in preparing nonfunctionalizedGTP (GTP-H), highlighting that microwave-assisted reactionsare particularly effective for the decarboxylation of carboxyl-functionalized GTP. The ionic conductivity of GTP-N-Bu·TFSIwas found to be comparable to that of the reference polymerGP-Im-Bu·TFSI, while GTP-N-EG3·TFSI exhibited higher ionicconductivity than the reference polymer GTP-(N-Me)-EG3·TFSI.These results suggested that reducing steric crowding around thetriazolium unit is crucial for enhancing ionic conductivity. Thesefindings contribute to the development of a facile synthesis forGTP-based poly(ionic liquid)s with improved ionic conductiveproperties.4. Experimental SectionSynthesis of GTP-COOH: PECH was cut into small pieces (<10 mm3)to fascinate the dissolution. PECH (3.0 g, 32 mmol monomer unit) andNaN3 (3.0 g, 46 mmol) were suspended in dry DMF (60 mL) in a 500-mL round bottom flask. After 10 min N2 bubbling of the solution at roomtemperature with stirring, the mixture was stirred at 90 °C under N2 at-mosphere for 24 h. After cooling to room temperature, the solution wasdiluted and centrifuged (5000 rpm, 10 min). The supernatant was vacuum-filtrated through alumina powder (Al2O3 for column chromatography;Note: Alumina is inert to NaN3 under ordinary condition.).[55] The solu-tion was concentrated to the original volume (60 mL) with an evaporator.After 10 min N2 bubbling of the solution at room temperature with stir-ring, distilled propiolic acid (4.2 mL, 68 mmol) was added. The mixturewas stirred at 50 °C under N2 atmosphere for 3 d. After cooling to roomtemperature, the solution was concentrated to the half volume with anevaporator. The solution was added dropwise in MeOH (600 mL) withstirring for precipitating the product. After rinsing with MeOH, the prod-uct was dried under vacuum overnight at 80 °C. The product was obtainedas a white solid. Yield: 5.0 g (91%). 1H NMR (400 MHz, DMSO-d6): 𝛿 =3.00–4.10 (multiple broad peaks, 3H), 4.10–4.90 (multiple broad peaks,2H), 8.01 (br, 0.12 H, triazole of 5-functionalized product), 8.58 (br, 0.88H, triazole of 4-functionalized product); 13C NMR (100 MHz, DMSO-d6):𝛿 = 50.6, 67.0–69.0, 77.0, 129.6, 139.8, 161.8.Synthesis of GTP-H: GTP-COOH was grinded into powder with a mor-tar. In order to prevent over-heating of the reaction solution by microwaveirradiation, GTP-COOH (1.0 g, 5.9 mmol) was completely dissolved in dryDMF (15 mL) at 60 °C with an aluminum heating/reaction block. Aftersetting the solution to the microwave reactor, the reaction temperaturewas gradually raised with increasing the irradiation power (20 → 40 W)with stirring. The solution was allowed to react at 150 °C for 1 h. Aftercooling to room temperature, the solution was concentrated to 5 mL byevaporation. The solution was added dropwise to diethyl ether (100 mL)for precipitating the product with stirring in a 500-mL PTFE beaker. Afterrinsing with diethyl ether, the product was dried under vacuum overnightat 80 °C. The product was obtained as a pale yellow solid. Yield: 0.65 g(88%). 1H NMR (400 MHz, DMSO-d6): 𝛿 = 3.15–3.50 (br, overlapping towater peak), 3.73 (br, 1H), 4.20–4.48 (br, 2H), 7.70 (br, 1H), 8.02 (br, 1H);13C NMR (100 MHz, DMSO-d6): 𝛿 = 50.3, 68.1–68.9, 77.5, 125.9, 133.4.Synthesis of Cationic GTPs: As a representative of cationic GTPs, thesynthetic procedure for GTP-N-Et·TFSI is described as follows. GTP-H(0.61 g, 4.9 mmol) and iodoethane (2.0 mL, 25 mmol) were dissolved indry DMF (6 mL). The mixture was stirred at 70 °C under N2 atmospherefor 24 h. After cooling to room temperature, distilled water was added(100 mL). The aqueous solution was washed with CH2Cl2 (100 mL × 3) byshaking in a separation funnel. For quick phase separation, the mixed solu-tion was subjected to centrifugation (5000 rpm, 5 min). The organic layerwas discarded. The aqueous layer was treated with activated carbon (5 g).After filtration, Li·TFSI (2.5 g/ 10 mL distilled water) was added to the so-lution with stirring. After 30 min, the product was recovered by centrifuga-tion (5000 rpm, 5 min). The recovered product was dissolved in acetone.The acetone solution was concentrated with an evaporator (5 mL). Theacetone solution was added dropwise to the aqueous solution containingLi·TFSI (2.5 g). After 30 min, the product was recovered by centrifugation(5000 rpm, 5 min). After rinsing with distilled water, the recovered productwas dissolved in acetone. The solution was dried with MgSO4, filtrated andconcentrated. The product was dried under vacuum overnight at 80 °C.GTP-N-Et·TFSI: 1H NMR (400 MHz, CD3CN): 𝛿 = 1.61 (t, J = 7.4 Hz,3H), 3.37–4.00 (br, 3H), 4.50–4.84 (m, 4H), 8.33 (m, 1H), 8.41 (m, 1H);13C NMR (100 MHz, CD3CN): 𝛿 = 14.6, 50.7, 55.2, 67.9, 76.0–77.2, 120.8(q, J = 319 Hz), 131.2, 132.6.GTP-N-Bu·TFSI: 1H NMR (400 MHz, CD3CN): 𝛿 = 0.96 (t, J = 7.0 Hz,3H), 1.39 (m, 2H), 1.96 (overlapping to acetonitrile), 3.37–4.00 (broadmultiple peaks, 3H), 4.50–4.84 (overlapping multiple peaks, 4H), 8.34 (m,1H), 8.40 (m, 1H); 13C NMR (100 MHz, CD3CN): 𝛿 = 13.6, 20.0, 31.8, 54.9,55.3, 67.9, 76.4–77.4, 120.9 (q, J = 319 Hz), 131.5, 132.6.GTP-N-EG3·TFSI: 1H NMR (400 MHz, CD3CN): 𝛿 = 3.28 (s, 3H),3.35–3.85 (multiple peaks, 10H), 3.85–4.10 (overlapping peaks, 3H), 4.50–4.84 (overlapping multiple peaks, 4H), 8.36 (m, 1H), 8.59 (m, 1H); 13CNMR (100 MHz, CD3CN): 𝛿 = 54.9, 55.3, 58.9, 67.9, 68.4, 70.7, 70.8, 71.0,72.5, 76.5–77.5, 120.9 (q, J = 319 Hz), 132.3, 132.6.Supporting InformationSupporting Information is available from the Wiley Online Library or fromthe author.AcknowledgementsThis work was financially supported by Grant-in-Aids for Scientific Re-search C, 22K05246 (JSPS).Conflict of InterestThe authors declare no conflict of interest.Data Availability StatementThe data that support the findings of this study are available in the Sup-porting Information of this article.Keywordsglycidyl triazolyl polymers, ion conductive materials, microwave reaction,poly(ionic liquid)s, polyelectrolytesMacromol. 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See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.mrc-journal.de Copper-Free Synthesis of Cationic Glycidyl Triazolyl Polymers 1. Introduction 2. Results and Discussion 2.1. Synthesis of Cationic GTPs 2.2. Thermal Properties 2.3. Ionic Conductivity 3. Conclusion 4. Experimental Section Supporting Information Acknowledgements Conflict of Interest Data Availability Statement Keywords