# Fileset

[2025-JPolymSci.pdf](https://mdr.nims.go.jp/filesets/d71fa0fe-ef63-4a94-8356-0d72b8acc0b0/download)

## Creator

[Taichi Ikeda](https://orcid.org/0000-0001-6650-5798), [Naoe Hosoda](https://orcid.org/0000-0002-7440-4927)

## Rights

[Creative Commons BY Attribution 4.0 International](https://creativecommons.org/licenses/by/4.0/)

## Other metadata

[Facile, Efficient, and Safe Copper‐Free Synthesis of Glycidyl Triazolyl Polymers](https://mdr.nims.go.jp/datasets/ffc87c6c-7469-42b8-8a4a-9a2bdf8cc41c)

## Fulltext

Facile, Efficient, and Safe Copper‐Free Synthesis of Glycidyl Triazolyl PolymersJournal of Polymer Science, 2025; 63:2568–2578https://doi.org/10.1002/pol.202502332568Journal of Polymer ScienceRESEARCH ARTICLE OPEN ACCESSFacile, Efficient, and Safe Copper-Free Synthesis of Glycidyl Triazolyl PolymersTaichi Ikeda1   |  Naoe Hosoda2,31Research Center for Macromolecules and Biomaterials, National Institute for Materials Science, Tsukuba, Japan  |  2Research Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba, Japan  |  3Tokyo University of Technology, Hachioji, JapanCorrespondence: Taichi Ikeda (ikeda.taichi@nims.go.jp)Received: 27 February 2025  |  Revised: 21 April 2025  |  Accepted: 21 April 2025Funding: This work was supported by Cabinet Office, Government of Japan, 24126704, Japan Society for the Promotion of Science, 22K05246.Keywords: azide-alkyne cycloaddition | click chemistry | glycidyl triazolyl polymers | polyethers | post-functionalization of polymersABSTRACTIn this study, a new synthetic procxe was proposed to solve the problems in the conventional copper-free glycidyl triazolyl pol-ymer (GTP) synthesis: (1) the explosion risk of the solid glycidyl azide polymer (GAP) and (2) large material loss of the electron-deficient alkyne derivative. In order to demonstrate the superiority of the new synthetic procedure, five kinds of GTPs were synthesized with different types of alkyne derivatives. GAP was synthesized through the reaction between polyepichlorohy-drin and sodium azide in N,N-dimethylformamide. For handling impact- and friction-sensitive solid GAP safely, it was purified through liquid–liquid extraction and stored as a stock solution without isolating it in the solid state. Through the new procedure utilizing a stock solution, the reaction efficiency in GTP synthesis was greatly improved, which resulted in reducing material loss (Feed ratio alkyne/azide: from 4.0 to 1.3) and reaction time (from 72 to 24 h). Thanks to the facile, efficient, and safe synthetic method, enough amounts of GTP samples could be prepared for characterizing not only physicochemical properties (density, molecular weight, glass transition temperature, thermal decomposition temperature, surface free energy) but also mechanical properties (Young's modulus, fracture stress and strain). The synthetic procedure reported herein will accelerate the research and development of functional GTPs with tunable physical properties.1   |   IntroductionThe physical properties of polymer materials depend on the poly-mer design [1–5]. Although the number of polymers that poly-mer chemists can imagine is nearly infinite, the actual number of polymers that can be synthesized is limited. With the boom of artificial intelligence (AI)-assisted materials design [6–10], it has become important to increase the design capability of poly-mers. In general, monomers with more complex structures are more difficult to polymerize. The post-functionalization method is an attractive way to expand the design capability of polymer materials because it can skip the obstacles faced in the polym-erization process [11–13]. In addition, post-functionalization en-ables us to prepare a series of polymer materials with the same degrees of polymerization distribution. When the polymer sam-ples are prepared using conventional polymerization methods, the reported physical properties are often different from each other because they have different degrees of polymerization; for instance, the reported values of glass transition temperature (Tg) of poly(n-octyl methacrylate) range from −45°C to −20°C [14, 15]. In the case of polymer samples prepared with the post-functionalization method, one can provide high-quality data sets for the machine learning of AI-assisted material design.Click-chemistry, which won the Nobel Prize in Chemistry 2022, is a powerful tool for post-functionalization [16, 17]. Among the reactions in click-chemistry, the copper-catalyzed azide-alkyne cycloaddition (Cu-AAC) reaction can provide efficient This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.© 2025 The Author(s). Journal of Polymer Science published by Wiley Periodicals LLC.https://doi.org/10.1002/pol.20250233https://doi.org/10.1002/pol.20250233mailto:https://orcid.org/0000-0001-6650-5798https://orcid.org/0000-0002-7440-4927mailto:ikeda.taichi@nims.go.jphttp://creativecommons.org/licenses/by/4.0/http://crossmark.crossref.org/dialog/?doi=10.1002%2Fpol.20250233&domain=pdf&date_stamp=2025-05-142569and functional-group-tolerant (orthogonal) chemistry for post-functionalization [17–22]. Polymer synthesis through post-functionalization with Cu-AAC boomed in the 2000s. However, an accident in a University of Minnesota lab in 2014 reminded chemists of the explosion hazards of azide compounds [23]. Given the above perspectives, the development of safer synthetic procedures is an important issue for the post-functionalization of polymers with AAC.Glycidyl triazolyl polymer (GTP) is a representative polymer synthesized through post-functionalization with Cu-AAC [24]. Since the first report by H. L. Cohen in 1981 [25], more than 80 types of GTPs, such as ion-conductive GTPs [26–29], GTPs with biocompatible properties  [30, 31], and GTPs with self-healing properties  [32], have been reported so far. A major advantage of GTP is the ready availability of the starting material polyepi-chlorohydrin (PECH), which is supplied as Hydrin. As a first step toward GTP, glycidyl azide polymer (GAP) is synthesized through the reaction between PECH and sodium azide (NaN3) in N,N-dimethylformamide (DMF) [25]. In our previous studies, GAP was recovered as a precipitate by adding the reaction solu-tion to water [26–29]. However, storing and handling GAP in the solid state is hazardous because GAP is known as an impact- and friction-sensitive material [33]. In addition, the solubility of solid GAP becomes worse as time goes by because the cross-linking reaction takes place between GAPs [25]. In our experience, GAP stored in the solid state for 2 weeks became less soluble in DMF. These issues concerning the solid GAP have long been an obsta-cle to accelerating the research and development of GTPs.As a final step, GTP is synthesized via a Cu-AAC reaction be-tween GAP and an alkyne derivative [26–32]. The use of a cop-per catalyst requires a time-consuming and stressful work-up procedure for purification. To address this issue, Cu-free syn-thesis of GTP was previously reported with an AAC reaction between an azide group and an electron-deficient alkyne de-rivative [25, 34, 35]. However, the results in the previous study discouraged us from exploring new GTPs with Cu-free synthe-sis because it required much larger amount of alkyne derivative (four equivalent to the azide group) and a long reaction time (72 h) [34].On the basis of these perspectives, a facile, efficient, and safe synthetic procedure for GTP synthesis was developed in this study. In order to demonstrate the superiority of the new proce-dure, five kinds of GTPs were synthesized with different types of alkyne derivatives (Figure 1). Octyl (C8), 2-ethyl-hexyl (2Et-C6), cis-3-octenyl (cis3-C8), 2-(2-methoxyethoxy)ethyl (EG2Me), and benzyl (Bz) groups were selected as the side groups for modu-lating the physical properties of GTPs. Those side groups were representatives of linear alkyl, branched alkyl, kink alkenyl, flexible ethylene oxide, and aromatic groups. Although poly-methacrylate derivatives with the C8, 2Et-C6, EG2Me, and Bz side groups have been reported so far [14, 36–38], there is no re-port on those with the cis3-C8 side group, indicating that the GTP synthesis reported herein can expand the design capabil-ity of polymer materials. Thanks to the facile synthetic method, enough amounts of GTP samples could be prepared to charac-terize not only physicochemical properties (density, molecular weight, glass transition temperature, thermal decomposition temperature, and surface free energy) but also mechanical prop-erties (Young's modulus, fracture stress, and strain).2   |   Results and Discussion2.1   |   Synthesis of Electron-Deficient AlkynesFigure  2a shows the synthetic route for the electron-deficient alkyne derivatives. In our previous study, electron-deficient alkyne derivatives were synthesized through a transesterifi-cation reaction between the alcohol and methyl propiolate in the presence of p-toluenesulfonic acid as an acid catalyst [34]. Despite the long reaction time (72 h), the product yield was low (43%). In this study, electron-deficient alkynes were synthesized through an esterification reaction between alcohol and propi-olic acid in the presence of cation exchange resin as an acid catalyst. We succeeded in reducing the reaction time (24 h) and improving the product yield. Because the product was obtained almost quantitatively (yield > 90%), the synthesis of alkyne-C8 and alkyne-2Et-C6 required no silica gel chromatography pu-rification. The synthesis of alkyne-EG2Me could also skip chromatography purification because the unreacted materials could be removed in a liquid–liquid partition process (toluene/water). In the cases of alkyne-cis3-C8 and alkyne-Bz, side reac-tions decreased the product yields and required chromatogra-phy purification. After the reaction, the cation exchange resin was recovered from the reaction solution by filtration. When the FIGURE 1    |    Chemical structures of GTPs. 26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License2570 Journal of Polymer Science, 2025reaction was carried out using the recovered cation exchange resin, the product yield decreased to 60%, confirming that the cation exchange resin could not be reused. The reaction tem-perature (100°C) is close to the upper limit of the suggested oper-ating condition of the resin (5°C–120°C). Thermal degradation is a possible reason for the performance deterioration of the resin as an acid catalyst.2.2   |   Cu-Free Synthesis of GTPsFigure  2b shows the synthetic route for the GTP derivatives. First, GAP was synthesized from PECH through a reaction with NaN3. Reportedly, the formation of hydrazoic acid through the reaction between water and NaN3 was a plausible cause of the explosion at the incident at the University of Minnesota in 2014 [23]. During the reaction, continuous N2 purge effectively prevented the accumulation of hydrazoic acid in the reaction solution because hydrazoic acid is easily volatile [39]. After the reaction was completed, the solution was cooled to room tem-perature and diluted with ethyl acetate. Then, distilled water (100 mL) was added to the reaction mixture with stirring to dis-solve salts (NaCl and unreacted NaN3). When the aqueous layer was collected using a separation funnel, its volume increased to ~170 mL, indicating that a large amount of DMF was partitioned to the aqueous layer. To prevent the formation of a highly con-centrated GAP solution, dry DMF (30 mL) was added before the evaporation. The solvent ethyl acetate was removed using an evaporator at 40°C under reduced pressure. Complete removal of ethyl acetate was confirmed by 1H NMR of the stock solution (data not shown). The weight of the GAP stock solution was ad-justed by adding dry DMF. In order to confirm the amount of GAP in the stock solution, solid GAP was recovered by adding 2.0 g GAP stock solution into distilled water. The weight of the recovered GAP was 0.128 ± 0.001 g (average ± standard error, n = 3), indicating 80.0 g stock solution contains ca. 5.1 g GAP.GTP was synthesized through a reaction between GAP and the electron-deficient alkyne derivatives. The reaction mixture was prepared by adding electron-deficient alkyne derivatives di-rectly to the stock solution of GAP. Compared with our previous study [34], the reaction time was shortened from 72 to 24 h. The feed ratio of alkyne to azide (alkyne/azide) was also improved from 4.0 to 1.3, which is a big advantage in decreasing the mate-rial loss of the alkyne derivatives. The key for improving the re-action efficiency was a higher reaction temperature (this study: 80°C; previous study: 60°C). In our previous study, the reaction temperature could not be raised to suppress the discoloration of GTP. In recent years, we empirically realized that salt contam-ination was one of the causes of discoloration. In the previous study, GAP was recovered as a precipitate by adding GAP solu-tion to water [26–29, 34]. In that case, the salt inside the solid GAP was difficult to remove completely. In order to confirm de-salination efficiency, the weight of the recovered salt through the work-up process was measured in 1.0 g scale GAP synthesis (see Supporting Information). In the case of the conventional procedure (precipitation in distilled water), the weight of the recovered salt was 0.82 ± 0.02 g (average ± standard error, n = 3). The new work-up procedure reported herein could recover 0.92 ± 0.00 g salts (average ± standard error, n = 3), which was close to the theoretical maximum of 0.93 g. The small standard error indicates that the new work-up procedure is reliable for complete removal of salts. The concentration of the solution was also an important factor in improving the reaction efficiency (this study: 1.0 g GAP per 16 mL of DMF; previous study: 1.0 g GAP per 50 mL of DMF). In the previous study, a large amount of solvent was required to dissolve solid GAP. The stock solu-tion method reported herein contributed to improving not only the safety but also the efficiency of the reaction. As mentioned above, the solubility of the solid GAP became worse in 2 weeks because of the cross-linking reaction between GAPs [25]. When the stock solution was stored in a desiccator under dark, no dete-rioration was detectable in 2 weeks.FIGURE 2    |    Synthetic route for GTP. (a) Synthesis of electron-deficient alkyne derivatives. (b) Cu-free synthesis of GTP. 26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License2571The chemical structure of GTP was confirmed using 1H NMR, 13C NMR, and IR spectra. Figure 3 shows the 1H NMR spec-trum of GTP-cis3-C8. The peaks were assigned with the help of 2D COSY and HMQC spectra (Figures  S11 and S12). The integral value of each peak matches the chemical structure (Figure S13). The peaks of the glycidyl protons a and c and the triazole proton d were split because of the stereochemistry of the carbon b. From the integrals of the triazole peaks, the ratio of 1,4-substituted and 1,5-substituted GTPs was calculated to be 9:1. The formation of structural isomer was a drawback of Cu-free synthesis of GTP [34, 35]. It was confirmed that the ratio of 1,4- and 1,5-substituted products was almost indepen-dent of the reaction conditions and type of substituents in this study (Table 1). Figure S14 shows the IR spectra of GAP and GTPs. It was confirmed that the azide peak (ν = 2100 cm−1) dis-appeared in the spectra of GTPs, indicating quantitative con-version from the azide group to the triazole group. All GTPs exhibited a characteristic strong peak at 1728 cm−1 based on C  O stretching.The densities of PECH, GAP, and GTPs are summarized in Table 1. The density of PECH was comparable to the reported value (1.41 g cm−3) in the technical data sheet published by the vendor (Scientific Polymer Products). The density of GAP was also consistent with the literature value [33]. The densities of GTP-C8, GTP-2Et-C6, and GTP-cis3-C8 were around 1.15 g cm−3, which was comparable to that of Nylon 66 (1.14 g cm−3) [40]. GTP-EG2Me and GTP-Bz gave higher densities of around 1.30 g cm−3 because of the introduction of additional oxygen atoms and the aromatic group, respectively. These densities were comparable to that of polyether ether ke-tone (1.32 g cm−3) [41].Figure  4 shows the molecular weight distributions of PECH, GAP, and GTPs determined using size exclusion chromatogra-phy (SEC) with polystyrene standards. The number and weight average molecular weights (Mn and Mw) and polydispersity index (PDI) are summarized in Table 1. The Mn value of PECH was comparable to the reported value in the vendor's technical FIGURE 3    |    1H NMR spectrum of GTP-cis3-C8. (400 MHz, solvent: CDCl3). Assignments of peaks are also depicted.TABLE 1    |    Density, molecular weights, and thermal properties of PECH, GAP, and GTPs.Polymers Ratio of isomersa ρb [g cm−3] Mnc [g mol−1] Mwd [g mol−1] PDIe Tgf [°C] Td5g [°C]PECH — 1.40 6.6 × 105 3.7 × 106 5.5 −25 329GAP — 1.29 6.0 × 105 2.6 × 106 4.4 −43 219GTP-EG2Me 9:1 1.32 4.2 × 105 9.7 × 105 2.3 4 273GTP-cis3-C8 9:1 1.16 3.9 × 105 1.0 × 106 2.6 12 299GTP-2Et-C6 9:1 1.14 3.0 × 105 5.9 × 105 2.0 20 323GTP-C8 9:1 1.14 3.6 × 105 8.4 × 105 2.4 29 304GTP-Bz 9:1 1.31 4.4 × 105 9.6 × 105 2.2 63 265a1,4-substituted GTP: 1,5-substituted GTP.bDensity.cNumber average molecular weight.dWeight average molecular weight.ePolydispersity index.fGlass transition temperature (onset value).g5 wt% loss temperature (onset value). 26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License2572 Journal of Polymer Science, 2025data sheet (7.0 × 105 g mol−1, Scientific Polymer Products). The PDI values of PECH and GAP were very large, suggesting that these polymers would aggregate in the solution. The molecu-lar weights and PDI values of GTPs were smaller than those of PECH and GAP. This result also supports the speculation that PECH and GAP would aggregate in the solution. The same re-sults have been reported in our previous studies [26–29, 34, 35]. It was confirmed that the molecular weight distributions were similar for all GTPs. Looking into the detail, GTP-2Et-C6 exhib-ited the smallest Mn and PDI values among GTPs. The branched side chain is considered to be effective to suppress aggregation.2.3   |   Thermal Properties of GTPsThe thermal properties of PECH, GAP, and GTPs were char-acterized using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Figure S15 shows the DSC charts of PECH, GAP, and GTPs in the third heating cycle. The Tg values are summarized in Table 1. PECH and GAP were amor-phous rubber materials with Tg values of −25°C and −43°C, re-spectively. As for GAP, an exothermic peak was observed above 170°C due to the azide group decomposition.When the GTP sample solutions were added dropwise in the poor solvent (methanol or diethyl ether), some GTPs were recovered as white solid materials, indicating crystal domain formations. Figure  S16 shows the DSC charts of GTPs in the first heating cycle. GTP-2Et-C8, GTP-C8, and GTP-Bz clearly exhibited the endothermic peaks attributable to the melting of the crystal do-mains. In the third heating cycle in Figure S15, all DSC charts exhibited only heat capacity change based on the glass transition. After thermal treatment, samples became transparent, indicating that GTPs reported herein are amorphous materials and the crys-tal domains in GTPs are kinetically trapped metastable states. The Tg values of GTPs are summarized in Figure 5. The Tg val-ues were modulated around room temperature by changing the design of the side group. Compared with the linear alkyl chain (C8), the branched alkyl chain (2Et-C6) and the kink alkenyl chain (cis3-C8) decreased the Tg value. The flexible ethylene oxide chain (EG2Me) was the most effective in decreasing the Tg value. Meanwhile, the rigid aromatic ring of the benzyl group (Bz) in-creased the Tg value. As references, the Tg values of methacrylate polymers are also shown in Figure 5 [14, 36–38]. Except for the Bz side group, the Tg values of GTPs were much higher than those of the methacrylate polymers. This was attributed to much higher molecular weights of GTPs reported herein. The Mn values of the methacrylate polymers with EG2Me, 2Et-C6, and Bz groups were 2.7 × 104, 5.3 × 104, and 1.1 × 105 g mol−1, respectively [36–38].Figure  S17 shows the TGA charts of PECH, GAP, and GTPs. The 5 wt% loss temperatures (Td5) are summarized in Table 1. The Td5 value of PECH was above 300°C. As for GAP, a stepwise weight drop was observed in the temperature range from 180°C to 300°C. The weight loss in this step was 0.42, which is consis-tent with the weight loss of the azide group (molecular weights of azide group/monomer unit = 42.02/99.09 = 0.42). The Td5 val-ues of GTPs with the alkyl chains (C8 and 2Et-C6) were above 300°C. The Td5 value of GTP-cis3-C8 was also comparable to that of GTP-C8. Meanwhile, the ethylene oxide chain made the Td5 value worse. GTP-EG2Me lost 2 wt% mass up to 200°C, pre-sumably due to the evaporation of water. It was considered that the ether oxygen atoms of the ethylene oxide chains could catch water molecules. Compared with the methacrylate analogue, which was reported to be extremely hygroscopic [37], GTP-EG2Me exhibited little hygroscopic nature because it could form hydrophobic surfaces, as discussed below. GTP-Bz afforded the worst Td5 value (265°C) among GTPs reported in this study. The benzyl ester was susceptible to thermal decomposition, which was also reported for poly(benzyl methacrylate) [42].2.4   |   Mechanical Properties of GTPsThe mechanical properties of PECH and GTPs were charac-terized by tensile tests. The results are summarized in Table 2. FIGURE 4    |    Molecular weight distributions of GTPs. Polystyrene standard. (a) PECH. (b) GAP. (c) GTP-EG2Me. (d) GTP-cis3-C8. (e) GTP-2Et-C8. (f) GTP-C8. (g) GTP-Bz.FIGURE 5    |    Glass transition temperatures (Tg) of GTP derivatives and methacrylate polymers. The Tg values of methacrylate polymers are applied as representative reference values [14, 36–38]. No data was found for methacrylate polymer with a cis3-C8 side group. 26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License2573Figure  6 shows the stress–strain curves of GTPs. As shown in the inset photograph in Figure  6, the specimens of GTPs were transparent because they were amorphous polymers, as discussed above. It was confirmed that the mechanical prop-erties were linked to the glass transition temperature. GTPs with a higher glass transition temperature were harder; con-sequently, they exhibited smaller fracture strains and larger Young's moduli. In the cases of GTP-Bz and GTP-C8, the spec-imens fractured before yielding because their Tg values (63°C and 29°C, respectively) were higher than room temperature (16°C–17°C). In the case of GTP-2Et-C6, the specimen was fractured just after yielding because the Tg value (20°C) was near room temperature. In the case of GTP-cis3-C8, necking and strain hardening processes were observed because the Tg value (12°C) was below room temperature. The maximum stress was observed at the fracture strain. In the case of GTP-EG2Me, fracturing did not occur up to 700% strain. Because of its much lower Tg value (4°C) than room temperature, GTP-EG2Me was soft and easily deformed by stretching. Even if the stretch rate increased up to 100 mm min−1, fracturing was not observed. As a reference, the mechanical property of PECH was also characterized (Figure S18). Young's modulus of PECH was smaller than that of GTP-EG2Me because of its low Tg value.2.5   |   Surface Free Energy of GTPsThe surface free energies of PECH and GTPs were character-ized by contact angle measurements. From the contact angles obtained with water, ethylene glycol, and diiodomethane drop-lets, dispersive and polar components of the surface energy (γd and γp, respectively) were calculated [43]. The results are summarized in Table 3 and Figure 7. For all GTPs and PECH, dispersive interaction was the major component of the surface energy. The surface free energy of GTP-EG2Me was compara-ble to that of GTP-C8 even though GTP-EG2Me had a relatively polar ether oxygen group. It is considered that the surface free energy would be determined by the hydrophobicity of the ter-minal methyl group. In comparison, GTP-cis3-C8 and GTP-2Et-C6 gave higher surface energies. The introduction of a kink (cis3-C8) and branched (2Et-C6) points increased the degree of disorder, which might expose a relatively higher energy surface of the glycidyl triazolyl unit. GTP-Bz exhibited the highest sur-face energy among GTPs reported herein. The polymethacrylate analogs also showed a similar trend (diamond dots in Figure 7) TABLE 2    |    Mechanical properties of GTPs (average ± standard error, n = 3).Polymers E [MPa]a σf [MPa]b εf [%]c Tg [°C]dPECH 0.86 ± 0.01 > 0.8e > 700e −25GTP-EG2Me 2.9 ± 0.4 > 0.8e > 700e 4GTP-cis3-C8 100 ± 10 13 ± 1 570 ± 20 12GTP-2Et-C6 190 ± 10 14 ± 1 13 ± 1 20GTP-C8 410 ± 40 22 ± 1 9.3 ± 0.9 29GTP-Bz 870 ± 120 16 ± 1 3.3 ± 0.8 63aYoung's modulus.bFracture stress.cFracture strain.dGlass transition temperature.ePECH and GTP-EG2Me did not fracture up to 700% strain.FIGURE 6    |    Stress–strain curve of GTPs. Stretch rate: 10 mm min−1. Temperature: Room temperature (16°C–17°C). (a) GTP-EG2Me. (b) GTP-cis3-C8. (c) GTP-2Et-C6. (d) GTP-C8. (e) GTP-Bz. Inset photo-graph: Dumbbell-shaped specimens of GTPs.TABLE 3    |    Contact angle and surface free energy of GTPs (average ± standard error, n = 3).Polymers θwater [°]a θEG [°]b θDIM [°]c γd [mN m−1]d γp [mN m−1]ePECH 98.0 ± 1.4 68.2 ± 0.2 41.8 ± 3.8 32.2 ± 9.2 0.1 ± 0.7GTP-EG2Me 93.8 ± 0.2 70.4 ± 0.2 52.5 ± 1.5 19.4 ± 3.6 3.4 ± 1.5GTP-cis3-C8 88.9 ± 0.3 64.9 ± 0.1 55.0 ± 0.2 29.2 ± 4.8 1.2 ± 1.5GTP-2Et-C6 97.1 ± 0.8 73.7 ± 0.1 58.0 ± 0.6 29.8 ± 6.9 0.0 ± 0.1GTP-C8 96.2 ± 0.7 77.8 ± 1.2 66.5 ± 1.5 19.7 ± 5.3 2.4 ± 1.8GTP-Bz 80.4 ± 0.9 51.5 ± 0.1 31.8 ± 0.1 46.1 ± 1.0 0.1 ± 0.1aContact angle of water.bContact angle of ethylene glycol.cContact angle of diiodomethane.dDispersive component of the surface energy of GTP.ePolar component of the surface energy of GTP. Temperature: Room temperature (22°C–23°C). 26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License2574 Journal of Polymer Science, 2025[44–46]. It should be noted that GTP-EG2Me was insoluble in water despite poly(2-(2-methoxyethoxy)ethyl methacrylate) being water soluble [37]. These results indicate that GTPs exhibit unique physical properties that cannot be speculated from those of polymethacrylate analogs.3   |   ConclusionA facile, efficient, and safe synthetic procedure for GTPs was established. Compared to our previous study, the catalyst-free synthesis simplified the work-up process. A new synthetic procedure using a stock solution of GAP reduced the material loss and reaction time. Handling GAP in the solution state improved safety. This method was found to be effective for various types of alkyne derivatives, and the physicochemical and mechanical properties of GTP were successfully mod-ulated. The mechanical properties of GTPs depend on the glass transition temperature; that is, GTPs possessing higher glass transition temperatures exhibited higher Young's mod-uli and lower elasticities. Thanks to the post-functionalization method, the molecular weight distributions of the synthesized GTPs were comparable. This is a great advantage because the molecular weight dependence of the material properties can be neglected, allowing a rigorous discussion of structure–prop-erty relationships. In addition, high efficiency and orthogonal chemistry of AAC must increase the design capability of poly-mers. The synthetic procedure reported herein will accelerate the research and development of functional GTPs with tunable physical properties.FIGURE 7    |    Contact angles of water droplets on (a) PECH, (b) GTP-EG2Me, (c) GTP-cis3-C8, (d) GTP-2Et-C6, (e) GTP-C8, and (f) GTP-Bz films. (g) Surface free energy of PECH and GTP films. Diamond dots are plotted as reference data of poly(2-ethyl-hexyl methacrylate), poly(octyl methac-rylate), and poly(benzyl methacrylate) [44–46]. 26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License25754   |   Experimental Section/Methods4.1   |   MaterialsPolyepichlorohydrin (Average molecular weight: 700 kg mol−1) was purchased from Scientific Polymer Products Inc. Propiolic acid, diethylene glycol monomethyl ether, and cis-3-octen-1-ol were purchased from Tokyo Chemical Industry. Sodium azide (NaN3), sodium iodide (NaI), sodium hydroxide (NaOH), anhydrous magnesium sulfate (MgSO4), toluene, dichloro-methane, hexane, ethyl acetate, acetone, methanol, 1-octanol, 2-ethyl-1-hexanol, benzyl alcohol, activated carbon, and distilled water were purchased from Nacalai Tesque. Dry DMF was pur-chased from Kanto Chemical. Cation exchange resin Amberlite HPR2900 H hydrogen form was purchased from Merck. It was washed with distilled water and acetone, then dried under vac-uum before use. Polytetrafluoroethylene (PTFE) sheets (thick-ness: 1 mm) were purchased from AS ONE. Distilled water, ethylene glycol (99.5%) and diiodomethane (97%) for contact angle measurements were purchased from FUJIFILM Wako Pure Chemical.4.2   |   MethodsColumn chromatography was done by using Isolera Prime with Sfär Silica HC D flash chromatography cartridges (Biotage Co.). NMR spectra were recorded on a JEOL ECZ 400S (400 MHz and 100 MHz for 1H and 13C nuclei, respectively) with residual sol-vent as the internal standard. IR spectra were obtained using a Shimadzu IRSpirit-X with a KBr sample pellet. Size exclusion chromatography was carried out at 50°C with 0.01 M Li∙NTf2 in DMF as an eluent on a Shimadzu Nexera XR with a Shim-pack GPC-80MD column. Polystyrene standards (PStQuick A and B, Tosoh Bioscience) were used for molecular weight calibration. DSC was performed on Shimadzu DSC-60 Plus at a heating/cooling rate of 10°C min−1 under N2 flow. TGA was performed with Shimadzu DTG-60 under N2 flow. Aluminum sample pans were utilized and the heating rate was 10°C min−1 up to 550°C under N2 flow except for the case of GAP. As for GAP, ca. 2.5 mg sample was put in a platinum pan and the heating rate was set as follows: 25°C–180°C: 10°C min−1, 180°C–200°C: 2°C min−1, 200°C–250°C: 1°C min−1, 250°C–280°C: 2°C min−1, 280°C–550°C: 10°C min−1. Polymer density was determined via a sink–float method using NaI aqueous solutions at 20°C. The densities of the solutions were set in the range of 1.10–1.45 g mL−1 with a step of 0.01 g mL−1. Films of GTPs were prepared using the hot press machines MP-SCL and MP-SCH (Toyoseiki Co.). GTP samples were heated between two PTFE sheets at 100°C. The pressure was gradually increased up to 5 MPa in 5 min, and the sheets were then cooled to room tem-perature at 5 MPa. The thickness of the film was controlled with a stainless-steel spacer (Thickness: 0.5 mm). Test specimens for the tensile test were prepared by cutting out GTP films using an ISO 37-4 dumbbell-shaped cutter (Kobunshi Keiki Co.). The tensile test was conducted using a combination of the digital force gage ZTS-50N (Imada Co.) and the vertical motorized test stand MX2-500N (Imada Co.) at room temperature (16°C–17°C). Data were collected using the software Force Logger Next (Ver. 1.05, Imada Co.). The surface free energies of all materials were estimated from contact angle measurements using a drop shape analyzer (DSA25S, Krüss) and the Owens, Wendt, Rabel, and Kaelble method using distilled water, ethylene glycol, and diiodomethane [43]. The films were prepared by drop-casting dichloromethane solutions containing 10 wt% GTP samples on glass plates. The solvent was evaporated at room temperature inside a hood. The films were annealed at 150°C for 1 h and then cooled to room temperature. The laboratory conditions during the contact angle measurements were as follows: a temperature of 22°C–23°C and a relative humidity of 17%–19%.4.3   |   Synthesis4.3.1   |   Synthesis of Alkyne-C81-Octanol (13.0 g, 0.10 mol), cation exchange resin (2.5 g), and MgSO4 (5.0 g) were mixed in toluene (50 mL). After 10 min of N2 bubbling, distilled propiolic acid (9.2 mL, 0.15 mol) was added to the reaction mixture. The reaction solution was heated at 100°C under N2 atmosphere for 24 h. After cooling to room temperature, the resulting solid materials were removed by filtration. The solid materials on the filter paper were washed using 150 mL of tolu-ene during filtration. The filtrate was washed with distilled water (10 mL) and then with a NaOH aqueous solution (0.40 g/10 mL) using a separation funnel. The organic layer was recovered, dried with MgSO4, filtrated, and concentrated using an evaporator. The colorless liquid product was recovered through distillation (47°C at 2.3 Torr). Yield: 17.1 g (94%). 1H NMR (400 MHz, CDCl3, δ): 0.87 (t, J = 6.8 Hz, 3H), 1.20–1.40 (m, 10H), 1.66 (q, J = 7.2 Hz, 2H), 2.86 (s, 1H), 4.17 (t, J = 6.8 Hz, 2H); 13C NMR (100 MHz, CDCl3, δ): 14.2, 22.7, 25.9, 28.4, 29.2, 31.9, 66.6, 74.5, 74.9, 152.9.4.3.2   |   Synthesis of Alkyne-2Et-C62-Ethyl-1-hexanol (13.0 g, 0.10 mol), cation exchange resin (2.5 g), and MgSO4 (5.0 g) were mixed in toluene (50 mL). The reaction condition and work-up process were the same as Alkyne-C8. Distillation condition: 42°C at 2.3 Torr. Yield: 16.4 g (90%). 1H NMR (400 MHz, CDCl3, δ): 0.88 (t, J = 7.6 Hz, 6H), 1.22–1.42 (m, 8H), 1.61 (q, J = 6.0 Hz, 1H), 2.87 (s, 1H), 4.09 (q, J = 3.0 Hz, 2H); 13C NMR (100 MHz, CDCl3, δ): 11.0, 14.1, 23.0, 23.7, 29.0, 30.3, 38.7, 68.8, 74.5, 75.0, 153.1.4.3.3   |   Synthesis of Alkyne-EG2MeDiethylene glycol monomethyl ether (12.0 g, 0.1 mol), cation exchange resin (2.5 g), MgSO4 (5.0 g) were mixed in toluene (50 mL). The reaction condition and work-up process were the same as Alkyne-C8. Distillation condition: 70°C at 2.3 Torr. Yield: 13.5 g (78%). 1H NMR (400 MHz, CDCl3, δ): 2.94 (s, 1H), 3.32 (s, 3H), 3.49 (t, J = 4.6 Hz, 2H), 3.59 (t, J = 4.6 Hz, 2H), 3.67 (t, J = 4.6 Hz, 2H), 4.28 (t, J = 4.6 Hz, 2H); 13C NMR (100 MHz, CDCl3, δ): 59.0, 65.2, 68.5, 70.5, 71.8, 74.5, 75.4, 152.6.4.3.4   |   Synthesis of Alkyne-cis3-C8cis-3-Octen-1-ol (12.8 g, 0.10 mol), cation exchange resin (2.5 g), and MgSO4 (5.0 g) were mixed in toluene (50 mL). The reaction  26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License2576 Journal of Polymer Science, 2025condition and work-up process were the same as Alkyne-C8. Finally, the product was purified by column chromatography (Silica gel, Hexane/Ethyl acetate = 9/1). Distillation condition: 42°C at 2.3 Torr. Yield: 13.5 g (75%). 1H NMR (400 MHz, CDCl3, δ): 0.89 (t, J = 7.2 Hz, 3H), 1.25–1.38 (m, 4H), 2.04 (q, J = 6.8 Hz, 2H), 2.42 (q, J = 7.2 Hz, 2H), 2.87 (s, 1H), 4.18 (t, J = 7.0 Hz, 2H), 5.32 (q, J = 8.4 Hz, 1H), 5.53 (q, J = 8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3, δ): 14.1, 22.4, 26.7, 27.1, 31.8, 65.8, 74.7, 74.9, 123.5, 133.7, 152.8.4.3.5   |   Synthesis of Alkyne-BzBenzyl alcohol (10.8 g, 0.10 mol), cation exchange resin (2.5 g), and MgSO4 (5.0 g) were mixed in toluene (50 mL). The reaction condition and work-up process were the same as Alkyne-cis3-C8. Distillation condition: 59°C at 2.3 Torr. Yield: 9.5 g (59%). 1H NMR (400 MHz, CDCl3, δ): 2.91 (s, 1H), 5.23 (s, 2H), 7.33–7.43 (m, 5H); 13C NMR (100 MHz, CDCl3, δ): 68.0, 74.6, 75.2, 128.7, 128.8, 128.8, 134.6, 152.6.4.3.6   |   Synthesis of GAPPECH was cut into small pieces (< 10 mm3) to facilitate dissolu-tion. PECH (5.0 g, 0.054 mol repeating unit) was suspended in dry DMF (100 mL) in a 500 mL two-neck round-bottom flask with a condenser. After 10 min of N2 bubbling, NaN3 (5.0 g, 0.077 mol) was added to the solution at room temperature (note: A plastic spatula was used for weighing NaN3). The mixture was stirred at 90°C under N2 flow for 24 h. After cooling to room temperature, the solution was diluted with ethyl acetate (300 mL). Distilled water (100 mL) was added with stirring. The organic layer was recovered with a separation funnel, dried with MgSO4, and filtered. After adding 30 mL of dry DMF, ethyl ace-tate was completely removed using an evaporator at 40°C under reduced pressure. The weight of the solution was adjusted to 80.0 g by adding dry DMF. This stock solution contains ca. 5.1 g of GAP. The stock solution was stored at room temperature in a desiccator in the dark.4.3.7   |   Synthesis of GTP-C8After 10 min of N2 bubbling of the GAP stock solution (16.0 g, 10 mmol repeating unit), Alkyne-C8 (2.4 g, 13 mmol) was added to the solution. The reaction mixture was stirred at 80°C under an N2 atmosphere for 24 h. After cooling to room temperature, the solution was diluted with acetone (50 mL). The solution was then treated with activated carbon (2.0 g). The activated carbon was removed through filtration (Omnipore hydrophilic PTFE membrane; pore size: 0.45 μm). The solution was concentrated to 20 mL using an evaporator. The product was recovered as a pre-cipitate by adding the solution dropwise to methanol (300 mL) with stirring. The solvent was removed through decantation. The recovered product was dissolved in dichloromethane and concentrated to 20 mL through evaporation. The product was precipitated again in methanol (300 mL). After removing the solvent through decantation, the product was dried under vac-uum at 80°C. Yield: 2.6 g (93%). 1H NMR (400 MHz, CDCl3, δ): 0.84 (br, 3H), 1.10–1.50 (br, 10H), 1.72 (br, 2H), 3.10–4.00 (br, 3H), 4.29 (br, 2H), 4.30–4.85 (br, 2H), 8.08 (br, 0.09H), 8.25–8.75 (br, 0.91 H); 13C NMR (100 MHz, CDCl3, δ): 14.2, 22.7, 26.0, 28.6, 28.8, 29.3, 29.4, 31.9, 51.7, 65.6, 67.0–70.5 (br), 77.5–79.0 (overlap-ping to CDCl3 peak), 129.4, 140.1, 161.0.4.3.8   |   Synthesis of GTP-2Et-C6After 10 min N2 bubbling of the GAP stock solution (16.0 g, 10 mmol repeating unit), Alkyne-2Et-C6 (2.4 g, 13 mmol) was added to the solution. The reaction condition and work-up process were the same as GTP-C8. Yield: 2.6 g (92%). 1H NMR (400 MHz, CDCl3, δ): 0.85 (br, 6H), 1.16–1.50 (br, 8H), 1.68 (br, 1H), 3.10–4.00 (br, 3H), 4.21 (br, 2H), 4.32–4.80 (br, 2H), 8.07 (br, 0.09H), 8.32–8.72 (br, 0.91H); 13C NMR (100 MHz, CDCl3, δ): 11.0, 14.1, 23.0, 23.8, 29.0, 30.3, 38.8, 51.7 (br), 67.8, 67.0–70.5 (br), 77.5–78.5 (overlapping to CDCl3), 129.2, 140.1, 161.1.4.3.9   |   Synthesis of GTP-EG2MeAfter 10 min N2 bubbling of the GAP stock solution (16.0 g, 10 mmol repeating unit), Alkyne-EG2Me (2.2 g, 13 mmol) was added to the solution. The reaction condition was the same as GTP-C8. Although the work-up process was almost the same as GTP-C8, diethyl ether was used to precipitate the product instead of methanol. Yield: 2.5 g (92%). 1H NMR (400 MHz, CDCl3, δ): 3.10–4.00 (overlapping, 3H), 3.31 (br, 3H), 3.49 (br, 2H), 3.63 (br, 2H), 3.79 (br, 2H), 4.30–4.80 (overlapping, 2H), 4.46 (br, 2H), 8.13 (br, 0.10 H), 8.30–8.65 (br, 0.90 H); 13C NMR (100 MHz, CDCl3, δ): 51.6 (br), 59.0, 64.3, 67.0–70.5 (br), 69.0, 70.5, 71.9, 77.5–78.5 (overlapping to CDCl3), 129.7, 139.6, 160.8.4.3.10   |   Synthesis of GTP-cis3-C8After 10 min N2 bubbling of the GAP stock solution (16.0 g, 10 mmol repeating unit), Alkyne-cis3-C8 (2.4 g, 13 mmol) was added to the solution. The reaction condition and work-up process were the same as GTP-C8. Yield: 2.6 g (93%). 1H NMR (400 MHz, CDCl3, δ): 0.84 (br, 3H), 1.28 (br, 4H), 2.01 (br, 2H), 2.48 (br, 2H), 3.10–4.00 (br, 3H), 4.29 (br, 2H), 4.30–4.80 (br, 2H), 5.36 (br, 1H), 5.46 (br, 1H), 8.05 (br, 0.09 H), 8.30–8.75 (br, 0.91 H); 13C NMR (100 MHz, CDCl3, δ): 14.1, 22.4, 27.0, 27.1, 31.8, 51.6 (br), 64.8, 67.0–70.5 (br), 77.5–78.5 (overlapping to CDCl3), 123.8, 129.4, 133.4, 140.1, 160.9.4.3.11   |   Synthesis of GTP-BzAfter 10 min N2 bubbling of the GAP stock solution (16.0 g, 10 mmol repeating unit), Alkyne-Bz (2.2 g, 14 mmol) was added to the solution. The reaction condition was the same as GTP-C8. Although the work-up process was almost the same as GTP-C8, DMF was used to dilute the reaction solution instead of acetone. Yield: 2.4 g (93%). 1H NMR (400 MHz, CDCl3, δ): 3.00–3.90 (br, 3H), 4.10–4.80 (br, 2H), 5.27 (br, 2H), 7.15–7.40 (br, 5H), 8.05 (br, 0.09H), 8.20–8.60 (br, 0.91H); 13C NMR (100 MHz, CDCl3, δ): 51.4 (br), 66.9, 67.0–70.5 (br), 77.5–78.5 (overlapping to CDCl3), 128.5, 128.7, 128.9, 129.4, 129.7, 135.5, 139.7. 26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License2577AcknowledgmentsThis work was supported by Cross-ministerial Strategic Innovation Promotion Program (SIP), Challenge, Strategy, and Research & Development Plan for Social Implementation, 24126704; and Grant-in-Aids for Scientific Research C, 22K05246 (JSPS).References1. D. K. Schneiderman and M. A. Hillmyer, “Aliphatic Polyester Block Polymer Design,” Macromolecules 49 (2016): 2419–2428.2. H. Takahashi, I. Sovadinova, K. Yasuhara, S. Vemparala, G. A. Ca-puto, and K. Kuroda, “Biomimetic Antimicrobial Polymers—Design, Characterization, Antimicrobial, and Novel Applications,” Wiley Inter-disciplinary Reviews. Nanomedicine and Nanobiotechnology 15 (2023): e1866.3. I. Hamerton, B. J. Howlin, and V. Larwood, “Development of Quanti-tative Structure Property Relationships for Poly(Arylene Ether)s,” Jour-nal of Molecular Graphics 13 (1995): 14–17.4. T. Qu, G. Nan, Y. Ouyang, et al., “Structure–Property Relationship, Glass Transition, and Crystallization Behaviors of Conjugated Poly-mers,” Polymers 15 (2023): 4268.5. P. M. Hergenrother, “The Use, Design, Synthesis, and Properties of High Performance/High Temperature Polymers: An Overview,” High Performance Polymers 15, no. 1 (2003): 3.6. V. Liao, T. Myers, and A. Jayaraman, “A Computational Method for Rapid Analysis Polymer Structure and Inverse Design Strategy (RAP-SIDY),” Soft Matter 20 (2024): 8246–8259.7. Y. Zhao, R. J. Mulder, S. Houshyar, and T. C. Le, “A Review on the Ap-plication of Molecular Descriptors and Machine Learning in Polymer Design,” Polymer Chemistry 14 (2023): 3325–3346.8. Y. Amamoto, “Data-Driven Approaches for Structure-Property Rela-tionships in Polymer Science for Prediction and Understanding,” Poly-mer Journal 54 (2022): 957–967.9. K. Ishikiriyama, “Polymer Informatics Based on the Quantitative Structure-Property Relationship Using a Machine-Learning Frame-work for the Physical Properties of Polymers in the ATHAS Data Bank,” Thermochimica Acta 708 (2022): 179135.10. F. Cravero, M. F. Díaz, and I. Ponzoni, “Polymer Informatics for QSPR Prediction of Tensile Mechanical Properties. Case Study: Strength at Break,” Journal of Chemical Physics 156 (2022): 204903.11. K. A. Günay, P. Theato, and H.-A. Klok, “Standing on the Shoulders of Hermann Staudinger: Post-Polymerization Modification From Past to Present,” Journal of Polymer Science, Part A: Polymer Chemistry 51 (2013): 1.12. X. Chen and T. Michinobu, “Postpolymerization Modification: A Powerful Tool for the Synthesis and Function Tuning of Stimuli-Responsive Polymers,” Macromolecular Chemistry and Physics 223 (2022): 2100370.13. Y. Zhao, D. Li, and X. Jiang, “Chemical Upcycling of Polyolefins Through C−H Functionalization,” European Journal of Organic Chem-istry 26 (2023): e202300664.14. S. S. Rogers and L. Mandelkern, “Glass Transitions of the Poly-(n-Alkyl Methacrylates),” Journal of Physical Chemistry 61, no. 7 (1957): 985.15. H. A. Schneider, “Polymer Class Specificity of the Glass Tempera-ture,” Polymer 46 (2005): 2230–2237.16. H. C. Kolb, M. G. Finn, and K. B. Sharpless, “Click Chemistry: Di-verse Chemical Function From a Few Good Reactions,” Angewandte Chemie International Edition 40 (2001): 2004.17. M. Meldal, “Polymer Clicking by CuAAC Reactions,” Macromolecu-lar Rapid Communications 29 (2008): 1016–1051.18. V. V. Rostovtsev, L. G. Green, V. V. Fokin, and K. B. Sharpless, “A Stepwise Huisgen Cycloaddition Process: Copper(I)-Catalyzed Regiose-lective Ligation of Azides and Terminal Alkynes,” Angewandte Chemie, International Edition 41 (2002): 2596–2599.19. C. W. Tornøe, C. Christensen, and M. Meldal, “Peptidotriazoles on Solid Phase:  [1,2,3]-Triazoles by Regiospecific Copper(I)-Catalyzed 1,3-Dipolar Cycloadditions of Terminal Alkynes to Azides,” Journal of Organic Chemistry 67 (2002): 3057–3064.20. W. H. Binder and R. Sachsenhofer, “Click Chemistry in Polymer and Material Science: An Update,” Macromolecular Rapid Communications 29 (2008): 952–981.21. E. Haldón, M. C. Nicasio, and P. J. Pérez, “Copper-Catalysed Azide–Alkyne Cycloadditions (CuAAC): An Update,” Organic & Biomolecular Chemistry 13 (2015): 9528–9550.22. P. L. Golas and K. Matyjaszewski, “Marrying Click Chemistry With Polymerization: Expanding the Scope of Polymeric Materials,” Chemi-cal Society Reviews 39 (2010): 1338–1354.23. T. A. Taton and W. E. Partlo, “Chemical Safety: Explosion Hazard in Synthesis of Azidotrimethylsilane,” Chemical & Engineering News 92, no. 43 (2014): 2.24. T. Ikeda, “Glycidyl Triazolyl Polymers: Poly (Ethylene Glycol) Deriv-atives Functionalized by Azide–Alkyne Cycloaddition Reaction,” Mac-romolecular Rapid Communications 39 (2018): 1700825.25. H. L. Cohen, “The Preparation and Reactions of Polymeric Azides. II. The Preparation and Reactions of Various Polymeric Azides,” Jour-nal of Polymer Science, Part A: Polymer Chemistry 19 (1981): 3269.26. T. Ikeda, “Anionic Glycidyl Triazolyl Polymers: Oppositely Charged Analogs of Imidazolium-Based Cationic Glycidyl Triazolyl Polymers,” Macromolecules 56 (2023): 9229–9236.27. T. Ikeda, “Poly(Ionic Liquid)s With Branched Side Chains: Polymer Design for Breaking the Conventional Record of Ionic Conductivity,” Polymer Chemistry 12 (2021): 711–718.28. M. M. Obadia, A. Jourdain, A. Serghei, T. Ikeda, and E. Drocken-muller, “Cationic and Dicationic 1,2,3-Triazolium-Based Poly(Ethylene Glycol Ionic Liquid)s,” Polymer Chemistry 8 (2017): 910–917.29. T. Ikeda, S. Moriyama, and J. Kim, “Imidazolium-Based Poly(Ionic Liquid)s With Poly(Ethylene Oxide) Main Chains: Effects of Spacer and Tail Structures on Ionic Conductivity,” Journal of Polymer Science, Part A: Polymer Chemistry 54 (2016): 2896–2906.30. C. Kim, K. Kwon, J. Lee, H. Kim, K.-H. Chae, and M. Ree, “Well-Defined Biomimicking Brush-Polymer Self-Assemblies Revealing Cholesterol-And Phosphorylcholine-Enriched Surface,” Macromole-cules 50 (2017): 6489.31. J. Lee, J. C. Kim, H. Lee, S. Song, H. Kim, and M. Ree, “Self-Assembling Brush Polymers Bearing Multisaccharides,” Macromolec-ular Rapid Communications 38 (2017): 1700013.32. D. Liu, D. Wang, M. Wang, et al., “Supramolecular Organogel Based on Crown Ether and Secondary Ammoniumion Functionalized Glyc-idyl Triazole Polymers,” Macromolecules 46 (2013): 4617.33. T. Jarosz, A. Stolarczyk, A. Wawrzkiewicz-Jalowiecka, K. Pawlus, and K. Miszczyszyn, “Glycidyl Azide Polymer and Its Derivatives-Versatile Binders for Explosives and Pyrotechnics: Tutorial Review of Recent Progress,” Molecules 24 (2019): 4475.34. T. Ikeda, “Copper-Free Synthesis of Glycidyl Triazolyl Polymers,” Macromolecular Chemistry and Physics 219 (2018): 1800147.35. T. Ikeda, “Copper-Free Synthesis of Cationic Glycidyl Triazolyl Polymers,” Macromolecular Rapid Communications 45 (2024): 2400416. 26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License2578 Journal of Polymer Science, 202536. C. L. Elkins, T. Park, M. G. Mckee, and T. E. Long, “Synthesis and Characterization of Poly(2-Ethylhexyl Methacrylate) Copolymers Con-taining Pendant, Self-Complementary Multiple-Hydrogen-Bonding Sites,” Journal of Polymer Science, Part A: Polymer Chemistry 43 (2005): 4618.37. S. Han, M. Hagiwara, and T. Ishizone, “Synthesis of Thermally Sensitive Water-Soluble Polymethacrylates by Living Anionic Polymer-izations of Oligo(Ethylene Glycol) Methyl Ether Methacrylates,” Macro-molecules 36 (2003): 8312–8319.38. K. Koike, Q. Du, S. Nishino, and Y. Koike, “Light Scattering of Ideal Random Copolymers in Bulk,” Polymer 55 (2014): 878–885.39. D. S. Treitler and S. Leung, “How Dangerous Is Too Dangerous? A Perspective on Azide Chemistry,” Journal of Organic Chemistry 87 (2022): 11293–11295.40. Z. Chen, X. Liu, R. Lü, and T. Li, “Friction and Wear Mechanisms of PA66/PPS Blend Reinforced With Carbon Fiber,” Journal of Applied Polymer Science 105 (2007): 602–608.41. C. R. C. Lima, M. A. R. Mojena, C. A. D. Rovere, N. F. C. de Souza, and H. D. C. Fals, “Slurry Erosion and Corrosion Behavior of Some En-gineering Polymers Applied by Low-Pressure Flame Spray,” Journal of Materials Engineering and Performance 25 (2016): 4911–4918.42. K. Demirelli, M. Coskun, and E. Kaya, “Polymers Based on Benzyl Methacrylate: Synthesis via Atom Transfer Radical Polymerization, Characterization, and Thermal Stabilities,” Journal of Polymer Science, Part A: Polymer Chemistry 42 (2004): 5964.43. D. K. Owens and R. C. Wendt, “Estimation of the Surface Free Energy of Polymers,” Journal of Applied Polymer Science 13 (1969): 1741–1747.44. S. Wu, “Organic Coatings and Plastics Chemistry,” 1971, 31, 27.45. K. Kamagata and M. Toyama, “Effect of the Length of Branches on the Critical Surface Tension of Poly(n-Alkyl Methacrylates) and Copo-lymers of Stearyl Methacrylate With Methacrylonitrile,” Journal of Ap-plied Polymer Science 18 (1974): 167–178.46. M. Toyama, A. Watanabe, and T. Ito, “Surface Wettability of Alkyl Methacrylate Polymers and Copolymers,” Journal of Colloid and Inter-face Science 47 (1974): 802–803.Supporting InformationAdditional supporting information can be found online in the Supporting Information section.   26424169, 2025, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pol.20250233 by National Institute For, Wiley Online Library on [15/06/2025]. 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 License Facile, Efficient, and Safe Copper-Free Synthesis of Glycidyl Triazolyl Polymers ABSTRACT 1   |   Introduction 2   |   Results and Discussion 2.1   |   Synthesis of Electron-Deficient Alkynes 2.2   |   Cu-Free Synthesis of GTPs 2.3   |   Thermal Properties of GTPs 2.4   |   Mechanical Properties of GTPs 2.5   |   Surface Free Energy of GTPs 3   |   Conclusion 4   |   Experimental Section/Methods 4.1   |   Materials 4.2   |   Methods 4.3   |   Synthesis 4.3.1   |   Synthesis of Alkyne-C8 4.3.2   |   Synthesis of Alkyne-2Et-C6 4.3.3   |   Synthesis of Alkyne-EG2Me 4.3.4   |   Synthesis of Alkyne-cis3-C8 4.3.5   |   Synthesis of Alkyne-Bz 4.3.6   |   Synthesis of GAP 4.3.7   |   Synthesis of GTP-C8 4.3.8   |   Synthesis of GTP-2Et-C6 4.3.9   |   Synthesis of GTP-EG2Me 4.3.10   |   Synthesis of GTP-cis3-C8 4.3.11   |   Synthesis of GTP-Bz Acknowledgments References