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[Taichi Ikeda](https://orcid.org/0000-0001-6650-5798), [Masafumi Yoshio](https://orcid.org/0000-0002-1442-4352)

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[Fluorinated Glycidyl Triazolyl Polymers Exhibiting Thermally Stable Layered Structures and Sticky Hydrophobic Surfaces](https://mdr.nims.go.jp/datasets/d3864e23-8d89-4f0c-9cbc-b35169e11f2a)

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Fluorinated Glycidyl Triazolyl Polymers Exhibiting Thermally Stable Layered Structures and Sticky Hydrophobic SurfacesFluorinated Glycidyl Triazolyl Polymers Exhibiting Thermally StableLayered Structures and Sticky Hydrophobic SurfacesTaichi Ikeda* and Masafumi YoshioCite This: ACS Appl. Polym. Mater. 2026, 8, 3023−3032 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: The side-chain fluorinated polymers bearing dieth-ylene glycol monomethyl ether (EG2) and perfluorohexyl (C6F13)side groups were synthesized using glycidyl triazolyl polymers(GTPs). These GTPs were prepared via catalyst-free azide−alkynecycloaddition between glycidyl azide polymers and electron-deficient alkyne derivatives. Postpolymerization functionalizationenabled the successful production of fluorinated GTP homopol-ymers and copolymers with molecular weights on the order of 105g mol−1. Compared to previously reported side-chain fluorinatedpolymers, the fluorinated GTPs, denoted as GTP-EG2-co-C6F13x(where x indicates the C6F13 content), display a range of distinctiveand superior properties. Notably, they form well-organized layeredstructures with thermal stability up to 240 °C, significantlysurpassing that of fluoropolymers with longer fluorocarbon chains such as C8F17 and C10F21. This improved thermal stability isattributed not only to the high molecular weight but also to the longer and more flexible repeating units of the GTP backbonecompared to vinyl-based polymers. The layered structures also serve as physical cross-links, contributing to higher storage modulus.The surface properties of the fluorinated GTPs were evaluated by contact angle measurements. Among them, GTP-EG2-co-C6F1325exhibits particularly distinctive surface behavior. During the advancing contact angle measurement, the water droplet showedpronounced stick-and-slip motion, with a maximum contact angle exceeding the superhydrophobic threshold of 150°. In contrast,the receding contact angle was below 10°, satisfying the criterion for superhydrophilicity. Notably, this sticky hydrophobicity wasachieved on the smooth surface (surface roughness <1 nm), offering promising advantages for practical applications requiring precisedroplet positioning and strong droplet adhesion.KEYWORDS: fluorinated polymers, liquid-crystal polymers, postpolymerization functionalization, click chemistry, contact angle hysteresis,sticky hydrophobic surface■ INTRODUCTIONSide-chain fluorinated polymers are a class of polymersfunctionalized with fluorocarbon side groups.1,2 Comparedwith commodity fluoropolymers such as polytetrafluoro-ethylene (PTFE) and polyvinylidene fluoride (PVDF),3 theyoffer enhanced structural and functional tunability throughvariation in side-group composition.4,5 Fluorocarbons possess arange of unique properties that are difficult to replicate withother chemical groups, including low surface energy,6−8distinctive ferroelectric behavior,9,10 exceptional chemical andthermal stability,11 and mesogenic characteristics that promoteliquid crystal formation.12,13 However, perfluoroalkyl sub-stances (PFAS) have faced criticism and strict regulationbecause of their environmental impact,14 particularly theirbioaccumulative potential.15,16 The tendency for bioaccumu-lation is strongly dependent on fluorocarbon chain length.Fluorocarbons with chain lengths equal to or shorter than theperfluorohexyl group (C6F13) have been reported to be lesstoxic and less biopersistent than longer fluorocarboncompounds.17,18According to previous reports, the C6F13 group lies at thethreshold of structural organization: polymers functionalizedwith fluorocarbon chains longer than C6F13 tend to formlayered structures, whereas those with shorter chains typicallyyield amorphous materials.19,20 For example, acrylic polymersbearing C6F13 side groups directly attached to the main chainfail to form organized structures.19,20 In contrast, introducingan N-methylsulfonamide spacer between the main chain andthe C6F13 group has been reported to promote structuralorganization.21,22 In general, shorter fluorocarbon chains resultReceived: December 1, 2025Revised: February 11, 2026Accepted: February 12, 2026Published: February 16, 2026Articlepubs.acs.org/acsapm© 2026 The Authors. Published byAmerican Chemical Society3023https://doi.org/10.1021/acsapm.5c04519ACS Appl. Polym. Mater. 2026, 8, 3023−3032This article is licensed under CC-BY 4.0Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on March 3, 2026 at 00:12:08 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Taichi+Ikeda"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Masafumi+Yoshio"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/acsapm.5c04519&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/aapmcd/8/4?ref=pdfhttps://pubs.acs.org/toc/aapmcd/8/4?ref=pdfhttps://pubs.acs.org/toc/aapmcd/8/4?ref=pdfhttps://pubs.acs.org/toc/aapmcd/8/4?ref=pdfpubs.acs.org/acsapm?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acsapm.5c04519?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://pubs.acs.org/acsapm?ref=pdfhttps://pubs.acs.org/acsapm?ref=pdfhttps://creativecommons.org/licenses/by/4.0/in lower thermal stability of the organized structures due toweaker fluorocarbon−fluorocarbon interactions. A straightfor-ward strategy to address this limitation is to increase themolecular weight of the polymer, which can enhanceproperties such as thermal stability and mechanical strength.However, synthesizing high-molecular-weight side-chain fluo-rinated polymers is challenging because conventional polymer-ization techniques often lead to premature precipitation causedby limited solubility, thereby hindering sufficient chaingrowth.19−22 Although specialized methods such as surface-initiated polymerization can produce high-molecular-weightside-chain fluorinated polymers,23 these techniques are notwidely accessible and are unsuitable for large-scale production.Consequently, a postpolymerization functionalization strategyoffers a practical and versatile alternative.24,25In this study, we developed a novel class of side-chainfluorinated polymers using glycidyl triazolyl polymers (GTP).GTP serves as a representative platform synthesized bypostpolymerization functionalization via azide−alkyne cyclo-addition click chemistry.26−30 Figure 1 illustrates the syntheticroute of the copolymers with diethylene glycol methyl etherand C6F13 side groups (GTP-EG2-co-C6F13x, where x denotesthe C6F13 content). Notably, complete side-chain functional-ization was achieved even when glycidyl azide polymer (GAP)was reacted exclusively with C6F13−alkyne, enabling thesynthesis of side-chain fluorinated homopolymer (GTP−C6F13) with molecular weight on the order of 105 g mol−1.The fluorinated GTPs reported herein exhibit a range ofdistinctive and enhanced properties compared with previouslyreported side-chain fluorinated polymers. Some GTPs formwell-organized layered structures with enhanced thermalstability up to 240 °C. These organized structures act asphysical cross-links, contributing to higher storage modulus.During the advancing contact angle measurement on the GTP-EG2-co-C6F1325 film, the water droplet showed pronouncedstick-and-slip motion, with a maximum contact angle exceed-ing the superhydrophobic threshold of 150°. In contrast, itsreceding contact angle was below 10°, satisfying the criterionfor superhydrophilicity. Notably, this sticky hydrophobicitywas achieved on the smooth surface (surface roughness <1nm). These findings are discussed in the context of thermal,structural, rheological, and surface characterizations.■ EXPERIMENTAL SECTIONSynthesis of C6F13−AlkyneTridecafluoro-1-n-octanol (18.2 g, 0.05 mol), cation exchange resin(1.6 g), and MgSO4 (2.5 g) were mixed in toluene (25 mL). Afterbubbling nitrogen through the mixture for 10 min, distilled propiolicacid (6.2 mL, 0.10 mol) was added. The reaction mixture was heatedat 100 °C under a nitrogen atmosphere for 24 h. After cooling toroom temperature, the resulting solids were removed by filtration.The solids collected on the filter paper were washed with 150 mL oftoluene during filtration. The filtrate was subsequently washed withaqueous NaOH (1.5 g/10 mL) and aqueous NaHCO3 (1.5 g/10 mL)using a separation funnel. Caution: Frequent venting of CO2 is necessaryto relieve pressure in the separation funnel caused by the reaction betweenpropiolic acid and NaHCO3. The cessation of CO2 evolution indicatescomplete neutralization of propiolic acid. The organic layer wascollected, dried over MgSO4, filtered, and concentrated using a rotaryevaporator. The crude product was purified by column chromatog-raphy (SiO2, hexane/ethyl acetate = 9:1). The colorless liquid productwas obtained by distillation (2.3 Torr, 50−55 °C). Yield: 13.7 g(66%). 1H NMR (400 MHz, CDCl3): δ = 2.52 (m, 2H), 2.93 (s, 1H),4.48 (t, J = 6.6 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ = 30.5 (t, J= 22 Hz), 58.0, 74.1, 75.8, 108−122 (multiple small peaks for CF2and CF3), 152.3.Preparation of GAP Stock SolutionPolyepichlorohydrin (PECH) was cut into small pieces to facilitatedissolution in the solvent. PECH (4.0 g, 43 mmol) and sodium azide(NaN3, 4.0 g, 62 mmol) were mixed in dry DMF (80 mL) in a 500mL two-neck round-bottom flask. A condenser was attached to thecenter neck. The reaction mixture was heated at 90 °C with stirringunder a stream of N2 (100 mL min−1) for 24 h in a fume hood. Aftercooling to room temperature, 320 mL of ethyl acetate was added withstirring, followed by the addition of 80 mL of distilled water. Themixture was transferred to a separation funnel, and the upper organiclayer was collected, dried over MgSO4, and filtered. Because asignificant amount of DMF partitioned into the aqueous layer, 40 mLof dry DMF was added to the solution. The ethyl acetate wasremoved by evaporation at 35 °C while the pressure was graduallyreduced to 1.6 kPa. The concentration by evaporation was stoppedonce DMF began to evaporate. The total mass of the solution wasadjusted to 64 g by adding dry DMF. For this purpose, the weight ofthe empty flask must be measured before starting the experiment. Itwas determined that the 8.0 g solution contained 0.51 g of GAP (5.1mmol repeating units).30 This stock solution of GAP was stored atroom temperature (approximately 20 °C) in the dark.GTP−C6F13 HomopolymerAfter bubbling nitrogen through the GAP stock solution (8.0 g, 5.1mmol repeating units) for 10 min, C6F13−alkyne (2.7 g, 6.5 mmol)was added. Since the addition of C6F13−alkyne induces precipitationof GAP, it was added dropwise over 1 min. The reaction mixture wasstirred at 80 °C under a nitrogen atmosphere for 24 h. During theFigure 1. Synthetic scheme of GTP-EG2-co-C6F13x. PECH: Polyepichlorohydrin. GAP: Glycidyl azide polymer. GTP: Glycidyl triazolyl polymer.(i) NaN3/DMF, 90 °C, 24 h. GAP was stored as a stock solution (solvent: DMF). (ii) 80 °C, 24 h.ACS Applied Polymer Materials pubs.acs.org/acsapm Articlehttps://doi.org/10.1021/acsapm.5c04519ACS Appl. Polym. Mater. 2026, 8, 3023−30323024https://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig1&ref=pdfpubs.acs.org/acsapm?ref=pdfhttps://doi.org/10.1021/acsapm.5c04519?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asreaction, the product became insoluble. The mixture was then dilutedwith dry DMF (50 mL) and stirred at 80 °C for 30 min, followed bydecantation to remove the solvent. The resulting solid was washedagain with DMF at 80 °C for 30 min, and the solvent was removed bydecantation. The same washing procedure was repeated usingdifferent solvents, acetone (×2), dichloromethane (×2), and diethylether (×2) at 40 °C. The final product was dried under vacuum at100 °C. Yield: 2.5 g (96%).GTP-EG2-co-C6F13x CopolymerThe synthesis and workup procedure for the copolymer GTP-EG2-co-C6F1375 followed the same protocol as that used for the GTP-C6F13homopolymer. For GTP-EG2-co-C6F1360, dichloromethane was notused for washing the sample because the copolymer was slightlysoluble in it. Since the other copolymers did not undergo phaseseparation during the reaction, the copolymer was recovered byprecipitation in methanol. The resulting solid was washed withmethanol (×2) and diethyl ether (×3), then dried under vacuum at80 °C. The reaction conditions are summarized in Table 1.GTP-EG2-co-C6F1375Yield: 2.2 g (97%).GTP-EG2-co-C6F1360Yield: 2.1 g (98%). 1H NMR (400 MHz, CDCl3): δ = 2.61 (br,1.2H), 3.20−4.00 (overlapping broad peaks, 6.6H), 4.30−4.85(overlapping broad peaks, 4H), 8.12 (br, 0.08H), 8.30−8.90 (br,0.92H); 13C NMR (100 MHz, CDCl3): δ = 30.5 (t, J = 21 Hz), 51.7,57.1, 58.9, 64.3, 68.0−70.0 (br), 69.0, 70.5, 71.9, 77.0−78.5 (br),106−122 (m), 129.6, 139.3, 139.8, 160.4, 160.8.GTP-EG2-co-C6F1350Yield: 1.9 g (97%). 1H NMR (400 MHz, CDCl3): δ = 2.61 (br,1.0H), 3.20−4.00 (overlapping broad peaks, 7.5H), 4.30−4.85(overlapping broad peaks, 4H), 8.12 (br, 0.08H), 8.30−8.90 (br,0.92H); 13C NMR (100 MHz, CDCl3): δ = 30.4 (t, J = 21 Hz), 51.6,57.1, 59.0, 64.3, 68.0−70.0 (br), 69.0, 70.5, 71.9, 77.0−78.5 (br),106−122 (m), 129.7, 139.3, 139.7, 160.4, 160.8.GTP-EG2-co-C6F1325Yield: 1.6 g (96%). 1H NMR (400 MHz, CDCl3): δ = 2.64 (br,0.5H), 3.20−4.00 (overlapping broad peaks, 9.8H), 4.30−4.85(overlapping broad peaks, 4H), 8.13 (br, 0.09H), 8.30−8.90 (br,0.91H); 13C NMR (100 MHz, CDCl3): δ = 30.4 (t, J = 21 Hz), 51.5,57.1, 59.0, 64.3, 68.0−70.0 (br), 69.0, 70.5, 71.9, 77.0−78.5 (br),106−122 (m), 129.7, 139.2, 139.7, 160.4, 160.8.■ RESULTS AND DISCUSSIONSynthesis of GTPsGAP was prepared by reacting PECH with NaN3, purified byliquid−liquid extraction, and stored as a stock solution. SinceGAP was not isolated in solid form, it can be handled safelydespite being a high-energy, azide-rich compound withpotential explosion hazards.31 Nevertheless, the inherent risksassociated with GAP should not be overlooked. Care must betaken to avoid contamination with metallic impurities duringpreparation, and the GAP solution should not be overlyconcentrated during evaporation.Quantitative conversion of chlorine groups to azide groupswas confirmed in our earlier works.26,32 GTPs were synthesizedvia a catalyst-free azide−alkyne cycloaddition between GAPand an electron-deficient alkyne (Figure S2).30 Reactionconditions are summarized in Table 1. All GTPs wereobtained in excellent yields exceeding 95%.The chemical structures of the GTPs were confirmed by IRand NMR spectroscopy. In the IR spectra, the absence of theazide absorption band at 2100 cm−1 indicated quantitativeconversion of azide groups to triazole rings (Figure S1).26Although the GTP−C6F13 homopolymer, GTP-EG2-co-C6F1375, and 60 copolymers underwent phase separationduring the reaction, the azide−alkyne cycloaddition proceededto completion. Because the phase-separated material appearedas a swollen gel, the alkyne compound was likely still able todiffuse into the gel and react with the remaining azide groups.All GTPs exhibited an intense characteristic peak at 1740cm−1, corresponding to ester C�O stretching. IR peakscorresponding to the glycidyl main chain, diethylene glycol,and fluorocarbon side chains overlapped in the fingerprintregion. The peaks at 734, 811, 1011, 1080, and 1145 cm−1(marked with stars in Figure S1) were assigned to C−Fstretching vibrations, as their intensities increased with C6F13content. The characteristic peak at 3134 cm−1 was attributed tothe �CH stretching vibration of the 1,2,3-triazole ring.33Figure 2 shows the 1H NMR spectra of GTP copolymers.Since the GTP−C6F13 homopolymer and GTP-EG2-co-C6F1375 copolymer were insoluble in common deuteratedsolvents, NMR characterization was not performed for thesesamples. The catalyst-free azide−alkyne cycloaddition yieldsstructural isomers bearing 1,4- and 1,5-substituted triazolerings. The peaks labeled d and e in Figure 2a were assigned tothe triazole protons of the 1,4- and 1,5-substituted products,respectively.30,34 Based on the integrals of these peaks, the ratioof 1,4- to 1,5-substituted triazole units was approximately 9:1.In many examples of Cu-free GTP synthesis,29,30,34 this isomerratio was found to be independent of both the side-chainstructures and the reaction conditions. The C6F13 content ineach copolymer was determined by comparing the integral ofthe overlapping peaks (c, f, and i) with that of peak j. TheC6F13 contents calculated from the 1H NMR spectra were 61%,51%, and 25% for GTP-EG2-co-C6F1360, 50, and 25,respectively. These values are in good agreement with thefeed ratios of the corresponding alkyne derivatives used in thesynthesis. 13C NMR of GTPs are shown in Figures S3−S5.Figure S6 shows the SEC traces of the GTPs used formolecular weight analysis. Based on the SEC data, the number-average molecular weight (Mn), weight-average molecularweight (Mw), and polydispersity index of GTP-EG2-co-C6F1325 were determined to be 3.3 × 105 g mol−1, 5.5 ×105 g mol−1, and 1.7, respectively (calibrated using polystyrenestandards). These values are comparable to those previouslyTable 1. Summary of GTP Synthesissample name GAPa (g) EG2-alkyne (g) C6F13−alkyne (g) ratio of alkynesb ratio of alkyne/azidec yield (%)GTP−C6F13 0.51 − 2.7 0:1 1.3 96GTP-EG2-co-C6F1375 0.51 0.28 2.1 1:3 1.3 97GTP-EG2-co-C6F1360 0.51 0.45 1.6 2:3 1.3 98GTP-EG2-co-C6F1350 0.51 0.56 1.4 1:1 1.3 97GTP-EG2-co-C6F1325 0.51 0.84 0.68 3:1 1.3 96aGAP was supplied as a stock solution. An 8.0 g stock solution contains 0.51 g GAP. bMolar ratio of EG2−alkyne/C6F13−alkyne. cMolar ratio ofalkyne compounds and azide group in GAP.ACS Applied Polymer Materials pubs.acs.org/acsapm Articlehttps://doi.org/10.1021/acsapm.5c04519ACS Appl. Polym. Mater. 2026, 8, 3023−30323025https://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfpubs.acs.org/acsapm?ref=pdfhttps://doi.org/10.1021/acsapm.5c04519?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asreported for GTP derivatives.30 No peak was observed forGTP-EG2-co-C6F1350. Several possible explanations mayaccount for this result: (i) incomplete dissolution of GTP-EG2-co-C6F1350 in the solvent (DMF); (ii) adsorption of thepolymer onto the column resin; or (iii) formation of self-assembled aggregates such as micelles due to its amphiphilicnature.35 Since investigating the cause of this behavior fallsoutside the scope of this study, further characterization was notpursued. As all GTPs were synthesized from the same GAPstock solution, the Mn and Mw values of GTP−C6F13homopolymer were estimated to be 5.1 × 105 g mol−1 and8.5 × 105 g mol−1, respectively. Notably, these values are 1order of magnitude higher than those reported for side-chainfluorinated polymers prepared via radical polymeriza-tion,18,21,36 demonstrating the superiority of the postpolyme-rization functionalization approach.Thermal Properties of GTPsThermal properties were characterized by differential scanningcalorimetry (DSC), and the results are summarized in Figure3a and Table 2. All DSC thermograms, except that of theGTP−C6F13 homopolymer, exhibited a change in heat capacityat the glass transition temperature (Tg). Previous studies havereported that the Tg of fluorinated homopolymers is oftendifficult to detect.21,25 Based on a comparison with the DSCthermogram of the GTP-EG2 homopolymer,30 the observedTg is attributed to the transition from the solid to the rubberystate, resulting from increased mobility of both the GTP mainchain and the EG2 side chains. All DSC thermograms, exceptthat of GTP-EG2-co-C6F1325, exhibited two endothermicpeaks. Similar thermograms have been reported by othergroups.12,21,22,36,37 These two peaks are attributed to phasetransitions from the solid or rubbery state to the smecticliquid-crystalline (LC) state (Tmeso) and from the LC state tothe isotropic state (Tiso). A cross-polarized optical microscopyimage of GTP-EG2-co-C6F1375 at 175 °C shows an oily streaktexture with distinct optical birefringence, indicating theformation of a layered LC phase (Figure 4a). Comparedwith results reported by other groups for C6F13- and evenlonger C8F17- and C10F21-side-chain fluorinated polymers, theTiso value observed in this study is significantly higher (othergroups: 60−210 °C; this study: >240 °C).19−22,25,36,37 Thesedifferences are attributed to the substantially higher molecularweight of the GTPs compared with previously reportedpolymers. The enthalpy changes at Tmeso and Tiso, denoted asΔHmeso and ΔHiso, respectively, were obtained from the DSCpeak areas and are summarized in Table 2. Thesethermodynamic parameters are discussed in detail below,alongside the XRD results.Figure 3b presents the thermogravimetric analysis (TGA)traces of the GTPs. The temperature corresponding to 5%weight loss is denoted as Td5. The GTP−C6F13 homopolymerexhibited no significant weight loss up to 300 °C (Td5 = 325°C, Table 2). The Td5 values increased with C6F13 content,suggesting that the fluorinated groups contribute to delayingthe thermal degradation of the GTPs.Organized Structure of GTPsX-ray diffraction (XRD) measurements were conducted toinvestigate the organized structures of GTPs. Figure 4b showsthe XRD profiles of GTP films measured at 38 °C afterannealing at temperatures above Tmeso. In the low-angle regionof the GTP−C6F13 homopolymer (Figure 4b, top), intensepeaks corresponding to a layered structure were observed,including second-, third-, and fourth-order reflections. Thelayer spacing, calculated from the average of these four peaks,was 3.2 nm. The layered structure was also confirmed by AFM(Figure 4c). The layer spacing of 3.2 nm is comparable to thatobtained by DFT calculations (Figure 4d). In the higher-angleregion, small but distinct peaks corresponding to d-spacings of5.0 Å and 4.7 Å were detected. The 5.0 Å spacing, frequentlyreported for side-chain fluorinated polymers, is attributed tothe crystalline ordering of fluorocarbon chains.19−21 Incontrast, the 4.7 Å spacing was tentatively assigned to thepacking of the 1,2,3-triazole rings, which has not previouslybeen observed in GTPs because they were amorphous.29,30This ordering of the 1,2,3-triazole rings is considered to beinduced by the packing of the C6F13 groups.GTP-EG2-co-C6F1375 and 60 copolymers also exhibitedintense diffraction peaks corresponding to layered structures(Figure 4b). However, no pronounced peaks associated withcrystalline ordering of the C6F13 groups were observed. AFMFigure 2. 1H NMR spectra of GTP copolymers (400 MHz, CDCl3).(a) GTP-EG2-co-C6F1360, (b) 50, and (c) 25 copolymers. Thelabeling scheme for peak assignment is shown at the top. Peakintegrals (overlapping peaks c, f, i, and peak j) for determiningcopolymer composition are written in red.Figure 3. (a) DSC thermograms of GTPs. The number inparentheses indicates the C6F13 content. Third heating cycle. Heatingrate: 10 °C min−1. (b) TGA traces of GTPs. Heating rate: 10 °Cmin−1. N2 atmosphere.ACS Applied Polymer Materials pubs.acs.org/acsapm Articlehttps://doi.org/10.1021/acsapm.5c04519ACS Appl. Polym. Mater. 2026, 8, 3023−30323026https://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig3&ref=pdfpubs.acs.org/acsapm?ref=pdfhttps://doi.org/10.1021/acsapm.5c04519?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asmeasurements revealed that identifying the organizedstructures became increasingly difficult as the C6F13 contentdecreased (Figure S8).Figure 4e shows the temperature-dependent XRD profiles ofthe GTP-EG2-co-C6F1360 film during heating from 38 to 175°C. Above the Tg, diffraction peaks corresponding to theTable 2. Thermal Properties of GTPssample name Tga (°C) Tmesob (°C) ΔHmeso (J g−1) Tisoc (°C) ΔHiso (J g−1) Td5d (°C)GTP−C6F13 − 174 12.8 ± 0.4 235 1.8 ± 0.0 325GTP-EG2-co-C6F1375 61 151 8.2 ± 0.4 244 2.2 ± 0.1 315GTP-EG2-co-C6F1360 50 132 3.1 ± 0.1 217 1.9 ± 0.0 300GTP-EG2-co-C6F1350 33 107 0.2 ± 0.0 168 0.8 ± 0.0 301GTP-EG2-co-C6F1325 17 − − − − 291GTP−EG2e 4 − − − − 273aGlass transition temperature (onset value from the third heating cycle in DSC). bTransition from the solid or rubber state to the liquid-crystallinestate (peak-top value from the third heating cycle in DSC). cTransition from the liquid-crystalline state to the isotropic state (peak-top value fromthe third heating cycle in DSC). dTemperature corresponding to 5% weight loss in TGA analysis. eData was taken from the ref 30.Figure 4. (a) Cross-polarized optical microscopy image of GTP-EG2-co-C6F1375 at 175 °C. (b) XRD profiles of GTP−C6F13 homopolymer, GTP-EG2-co-C6F1375, 60, and 50 copolymers at 38 °C. The number in parentheses indicates the C6F13 content. (c) AFM image of a GTP−C6F13 film onglass. Scan area: 400 nm × 400 nm. (d) Proposed layered structure of GTP−C6F13 homopolymer. The molecular structure was obtained by DFTcalculations (B3LYP/6-31G*). (e) Temperature-dependent XRD profiles of GTP-EG2-co-C6F1360 during heating from 38 to 175 °C.Figure 5. (a) Temperature-dependent viscoelastic properties of GTP-EG2-co-C6F1375, 50, and 25 copolymers. The number in parenthesesindicates the C6F13 content. For clarity, each data set is offset by 2 orders of magnitude. The storage (G′) and loss moduli (G″) are shown as solidand dashed curves, respectively. Tg, Tmeso, and Tiso are marked with black, green, and red arrows, respectively. Storage moduli at 100 °C are shownfor comparison. (b) Dumbbell-shaped specimens of GTP copolymers used for tensile test. (c) Stress−strain curves of GTP-EG2-co-C6F1325, and50 copolymers. Film thickness: 0.5 mm. Temperature: 16−17 °C.ACS Applied Polymer Materials pubs.acs.org/acsapm Articlehttps://doi.org/10.1021/acsapm.5c04519ACS Appl. Polym. Mater. 2026, 8, 3023−30323027https://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig5&ref=pdfpubs.acs.org/acsapm?ref=pdfhttps://doi.org/10.1021/acsapm.5c04519?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-aslayered structure remained intense (75 °C in Figure 4e). Thisresult demonstrates that, although the GTP backbone and EG2side chains recover segmental mobility at Tg, the mobility ofthe C6F13 groups remains limited, thereby preserving the well-defined layered structure. Although the absence of apronounced peak associated with C6F13 packing indicateslow crystalline ordering of the C6F13 groups, the ΔHmeso valuesuggests that the C6F13 groups were phase-segregated from theEG2 side groups and interacted with each other within thedomain. Above Tmeso, the diffraction peaks weakened,indicating that the melting of the C6F13 domains leads to aless-defined layered structure, and the copolymer transitionsinto a smectic liquid crystalline state (150 °C in Figure 4e).The ΔHmeso value decreased as the C6F13 content decreased,due to the reduced amount of C6F13 domains. In contrast, theΔHiso values were independent of the C6F13 content in thecases of the GTP−C6F13 homopolymer, GTP-EG2-co-C6F1375,and 60 copolymers. These results suggest that most of thepolymer chains in those GTPs formed layered structures andthat the ΔHiso values originated from their order−disordertransitions. Similar temperature-dependent XRD profilechanges were also observed for the other GTPs (Figure S7).In the case of GTP-EG2-co-C6F1350, the peak intensitycorresponding to the layered structure became weaker (Figure4b), indicating a low degree of structural organization andsuggesting that the majority of the copolymer had becomeamorphous. This result is consistent with the DSC data, whichshow small ΔH values at Tmeso and Tiso (Table 2). AFM imageof GTP-EG2-co-C6F1325 exhibited a completely flat surface,reflecting the amorphous nature of the polymer (Figure S8).Mechanical Properties of GTPsSince viscoelastic properties are sensitive to self-organizedstructures within polymeric materials, the GTPs were analyzedusing a rheometer. Representative temperature-dependentprofiles of the storage modulus (G′) and loss modulus (G″)are shown in Figure 5a. Although the measurements wereinitiated above the Tg, behavior near Tg appeared unreliabledue to slippage at the interface between the rheometer plateand the polymer sample. As the sample became tacky uponheating, reliable data could only be obtained at temperaturesabove those indicated by the asterisks in Figure 5a. For theGTP-EG2-co-C6F1375 copolymer (Figure 5a, top), the G′ valuedecreased at Tmeso, followed by a plateau region between 180and 240 °C. G′ exceeds G″ below Tiso, indicating that theorganized structures function as physical cross-links andcontribute to elastic properties in the GTPs. Upon transitionfrom the smectic LC state to the isotropic state, both G′ andG″ dropped sharply.Similar temperature-dependent rheological property changeswere observed for the GTP−C6F13 homopolymer and thecopolymers GTP-EG2-co-C6F1360 and 50 (Figures S10 and5a). Notably, GTP-EG2-co-C6F1375 exhibited a broadertemperature range for the smectic LC phase and a higherTiso than the GTP−C6F13 homopolymer. Generally, anincreased C6F13 content is expected to raise Tiso due to astronger driving force for self-organization. However, completefunctionalization with the C6F13 side groups may induceexcessive steric crowding and mechanical stress, whichdestabilize the organized structure. Incorporation of the EG2side groups likely relieves this stress, thereby stabilizing thelayered structures. Based on these considerations, one plausibleexplanation for the lower thermal stability of layered structuresin vinyl-based fluorinated polymer is the shorter, less flexiblerepeating unit (−C−C−) relative to the GTP backbone (−C−C−O−), which increases mechanical stress. Thus, GTP isconsidered advantageous for realizing side-chain fluorinatedpolymers with enhanced thermal stability.In the case of GTP-EG2-co-C6F1325 (Figure 5a, bottom),the values of G′ and G″ decreased almost monotonically withincreasing temperature. The G′ value temporarily exceeded theG″ value at low temperatures, suggesting that the long chainlength of GTP may enhance chain entanglement, which couldact as transient physical cross-linking points.From the G′ values at 100 °C, it is evident that G′ of theGTP copolymers increases significantly with C6F13 content(Figure 5a). The markedly higher G′ of GTP-EG2-co-C6F1375compared with the other copolymers is likely attributable notonly to its smaller temperature separation from Tg but also toits well-organized structure. The large G′ drop around Tmeso inGTP-EG2-co-C6F1375 also supports this idea.Figure 6. (a) Surface energies of GTP−C6F13 and GTP−EG2 homopolymers and copolymers, determined from the contact angles of water,ethylene glycol, and diiodomethane droplets using the OWRK method. Values represent mean ± standard deviation (n = 5). (b) Photographs ofwater droplets on GTP-EG2-co-C6F1325 (left) and GTP−C6F13 (right) films. Droplet volume: 2 μL. (c) Surface roughness of GTP films. Valuesrepresent mean ± standard deviation (n = 3). (d) AFM images of GTP-EG2-co-C6F1325 (left) and GTP−C6F13 (right) films used to characterizesurface roughness (scan area: 10 μm × 10 μm).ACS Applied Polymer Materials pubs.acs.org/acsapm Articlehttps://doi.org/10.1021/acsapm.5c04519ACS Appl. Polym. Mater. 2026, 8, 3023−30323028https://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig6&ref=pdfpubs.acs.org/acsapm?ref=pdfhttps://doi.org/10.1021/acsapm.5c04519?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asFigure 5b shows dumbbell-shaped specimens of GTP-EG2-co-C6F1325 and 50 copolymers. GTP copolymers with C6F13content higher than 50% were too brittle to fabricate intodumbbell-shaped specimens. Figure 5c shows the stress−strainprofiles of dumbbell-shaped specimens of GTP copolymers.Because the Tg of GTP-EG2-co-C6F1325 is close to roomtemperature, that sample exhibited stretchability exceeding400% strain. In contrast, GTP-EG2-co-C6F1350 was rigid andfractured below 3% strain. The Young’s moduli of GTP-EG2-co-C6F1325 and 50 were 0.47 ± 0.03 GPa and 0.93 ± 0.05 GPa,respectively (mean ± standard error, n = 3).Surface Properties of GTPsThe surface properties of the GTP−C6F13 and GTP−EG2homopolymers, as well as their copolymers, were characterizedby contact angle measurements. From the contact angles ofwater, ethylene glycol, and diiodomethane droplets (FigureS11), the dispersive and polar components of the surfaceenergy (γd and γp, respectively) were calculated using theOwens, Wendt, Rabel and Kaelble method (OWRKmethod).38−40 The results are summarized in Figure 6a andTable 3.The surface energies of the GTP−C6F13 and GTP−EG2homopolymers were 8.3 ± 2.6 mN m−1 and 31.0 ± 9.2 mNm−1, respectively. These values reflect the low surface energy ofthe fluorocarbon side groups and the hydrophilic nature of theethylene glycol side groups. The copolymers exhibited surfaceenergies comparable to that of the GTP−C6F13 homopolymer,indicating that their surfaces were predominantly covered withfluorocarbon chains. As shown in Figure 6b, the water contactangle of the GTP-EG2-co-C6F1325 film is comparable to that ofthe GTP−C6F13 homopolymer film, even though the C6F13side group is a minor component. Interestingly, the surfaceenergy of GTP-EG2-co-C6F1325 exhibits a markedly smallerpolar component (γp = 0.8 ± 0.2 mN m−1) than those of theother fluorinated copolymers (γp = 2.3−2.7 mN m−1).To examine the cause of this anomaly, surface roughness wascharacterized by AFM. Figures 6d and S9 shows AFM imagesof the GTP films. The results are summarized in Figure 6c andTable 3. The surface roughness of the GTP-EG2 homopol-ymer and GTP-EG2-co-C6F1325 (Ra < 1 nm) was much smallerthan that of the other samples (Ra = 4−15 nm, Table 3). Thisdifference arises from whether the material is fully amorphous.To rationalize the lower polar component of the surface energyobserved for the GTP-EG2-co-C6F1325 film, we propose thefollowing hypothesis. A completely flat surface can beuniformly covered with C6F13 side chains, leaving few defectsites that expose the hydrophilic components of the polymer.In contrast, nanometer-scale roughness increases the numberof defect sites, thereby exposing more hydrophilic units.The advancing and receding contact angles (θA and θR),corresponding to the contact angles measured during theinflation and deflation of a water droplet, respectively, werealso characterized (Figure S12).41,42 Figure 7a shows theadvancing contact angle profiles as a function of dropletvolume. With the exception of GTP-EG2-co-C6F1325, all GTPsurfaces exhibited constant θA values, and their baseline widthsincreased smoothly over the volume range of 5−10 μL (FigureS13a, left). The θA values of the GTP-EG2-co-C6F1375, 60, and50 copolymers were comparable. In contrast, GTP-EG2-co-Table 3. Summary of Sessile-Drop Contact Angles, Surface Energies, and Surface Roughnesssample name θwatera (°) θEGb (°) θDIMc (°) γdd (mN m−1) γpe (mN m−1) rcf Rag (nm)GTP−C6F13 116 ± 1 106 ± 2 99 ± 1 7.2 ± 1.9 1.2 ± 0.7 0.95 3.7 ± 0.4GTP-EG2-co-C6F1375 110 ± 1 101 ± 3 99 ± 1 7.1 ± 1.0 2.4 ± 0.7 0.99 5.6 ± 1.3GTP-EG2-co-C6F1360 108 ± 1 99 ± 1 98 ± 1 7.0 ± 1.6 2.3 ± 1.4 0.96 7.4 ± 1.4GTP-EG2-co-C6F1350 109 ± 2 97 ± 3 99 ± 1 7.0 ± 0.5 2.7 ± 0.6 0.99 14.8 ± 1.9GTP-EG2-co-C6F1325 117 ± 1 102 ± 1 100 ± 1 7.6 ± 0.4 0.8 ± 0.2 0.99 0.4 ± 0.1GTP−EG2 76 ± 1 54 ± 1 44 ± 4 19.0 ± 5.0 11.9 ± 4.2 0.98 0.3 ± 0.1aStatic contact angle of a water droplet (2 μL). bStatic contact angle of an ethylene glycol droplet (2 μL). cStatic contact angle of a diiodomethanedroplet (2 μL). Values are presented as mean ± standard deviation (n = 5). dDispersive component of the surface energy. ePolar component of thesurface energy. Measurements were conducted at 20 °C and 15−20% relative humidity. fCorrelation coefficient of the OWRK method fitting.gArithmetic mean roughness (area: 10 μm × 10 μm). Values are presented as mean ± standard deviation (n = 3).Figure 7. (a) Representative advancing contact angle profiles duringthe inflation of water droplets. The droplet volume was increased at arate of 0.1 μL s−1. The number in parentheses indicates the C6F13content. The inset photograph shows a water droplet exhibiting themaximum advancing contact angle on the GTP-EG2-co-C6F1325 film.(b) Representative receding contact angle profiles during the deflationof water droplets. The droplet volume was decreased at a rate of 0.1μL s−1. The inset photographs show water droplets on the GTP−C6F13 homopolymer film (top left) and on the GTP-EG2-co-C6F1325film (bottom right). Droplet volume: 11 μL.ACS Applied Polymer Materials pubs.acs.org/acsapm Articlehttps://doi.org/10.1021/acsapm.5c04519ACS Appl. Polym. Mater. 2026, 8, 3023−30323029https://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?fig=fig7&ref=pdfpubs.acs.org/acsapm?ref=pdfhttps://doi.org/10.1021/acsapm.5c04519?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asC6F1325 exhibited a distinctive stick-and-slip behavior (Figure7a). Because the baseline width remained constant and the θAvalue continued to increase until reaching a critical value, noplateau region appeared in the θA profile (Figure S13a, right).Therefore, for this sample, the θA value in Table 4 wasobtained by averaging the contact angles measured within the5−10 μL volume range. This stick-and-slip behavior wasconsistently observed across the entire GTP-EG2-co-C6F1325film surface. Notably, as shown in the inset photograph ofFigure 7a, the maximum advancing contact angle reached 160± 2°, surpassing the critical threshold of 150° typically used todefine superhydrophobicity.43Figure 7b shows the receding contact angle profiles as afunction of droplet volume. Within a certain volume range, thecontact line was moving on the surface and the water dropletmaintained a constant θR value (Figure S13b). Because the θRvalues ranged widely from less than 5° (GTP−EG2) to 80°(GTP−C6F13), it was not feasible to obtain all measurementswithin the same volume range. However, since the volumeranges used for calculating the θR value of each sample partiallyoverlapped, we considered the data to be mutually comparable.Unlike the advancing contact angle results, the GTPcopolymers exhibited distinct, intrinsic θR values thatdecreased as the C6F13 content decreased. Notably, the θRvalue on the GTP-EG2-co-C6F1325 surface was 7 ± 1°, fallingbelow the commonly accepted threshold of 10° used to definesuperhydrophilicity.44 It is considered that the superhydrophi-licity at the polymer/water interface and superhydrophobicityat the polymer/air interface is responsible for the distinctivestick-and-slip behavior on the surface of GTP-EG2-co-C6F1325.The contact angle hysteresis (Δθ), defined as the differencebetween the advancing and receding contact angles,45 issummarized in Table 4. Notably, GTP-EG2-co-C6F1325exhibited a large Δθ of 123°. If calculated using the maximumadvancing contact angle (θA‑max), Δθ would reach 153°. LargeΔθ values are often observed on rough surfaces, aphenomenon known as the rose petal effect, which someresearchers reproduce through surface micropatterning.46−49For instance, Su et al. reported a Δθ value of 156° for thesurface covered with polyelectrolyte-coated submicrometer-scale silica particles,50 while Mistura et al. reported Δθ valuesof 100−120° for the surface covered with electrospun polymernanofibers.51 Contact angle hysteresis can also be observed onflat surfaces, but a Δθ exceeding 100° is exceptionally rare. Forinstance, the Δθ values of poly(2-hydroxyethyl methacrylate),poly(acrylic acid), and polyacrylamide derivatives�those areknown to exhibit pronounced contact angle hysteresis�rangefrom 20° to 70°.52,53 Meanwhile, the reported Δθ values foramphiphilic fluorinated copolymers similar to our GTPs rangefrom 60° to 80°.54,55 The contact angle hysteresis is thought tooriginate from surface reconstruction driven by molecularinteractions between the polymer and water.45,52,55 The air−polymer interface is considered to be fully covered with C6F13groups, whereas upon contact with water, the polymer adopts aconformation in which the EG2 side groups are exposed to thepolymer/water interface. The amorphous domain is consideredto be more advantageous for surface reconstruction than theorganized domain, because conformation change is suppressedin the organized domain. Since the fraction of the amorphousdomain increases as the C6F13 content decreases, the Δθ valuecorrespondingly increases. The high mobility of the GTP-EG2-co-C6F1325 chains, enabled by a low Tg near room temperature,is also considered to promote surface reconstruction.■ CONCLUSIONUsing a postpolymerization functionalization approach, high-molecular-weight fluorinated GTPs bearing perfluorohexyl sidechains were successfully synthesized. These polymers exhibitexcellent thermal, mechanical, and surface properties. Theirenhanced thermal stability and tunable mechanical propertiesare particularly promising for applications in ferroelectricdevices. Among the synthesized GTPs, GTP-EG2-co-C6F1325showed especially distinctive surface behavior. Duringadvancing contact angle measurements, the water dropletexhibited pronounced stick-and-slip motion, with a maximumcontact angle exceeding 150°, while the receding contact angledropped below 10°. This large contact angle hysteresisproduces a sticky hydrophobic surface. Such sticky hydro-phobic surfaces are attractive for applications requiring precisedroplet positioning and strong droplet adhesion, includinghigh-resolution printing, microfluidic manipulation, biosensing,and wearable devices that operate under motion. Notably,GTP-EG2-co-C6F1325 can produce sticky hydrophobic surfacewithout any micropatterning, offering a significant advantagefor device fabrication. In the context of global PFASregulations, perfluorooctanesulfonic acid (C8F17SO3H) andits related compounds were listed in Annex A of the StockholmConvention in 2009, which identifies chemicals designated forglobal elimination. Perfluorohexanesulfonic acid (C6F13SO3H)and its related compounds were subsequently added to AnnexA in 2022. Although the tridecafluoro-1-n-octanol used in thisstudy is not included in Annex A, the development offunctional fluoropolymers with shorter fluorocarbon chains isan urgent and important challenge. Overall, this studydemonstrates that fluorinated GTPs are promising candidatesfor next-generation functional fluoropolymers. Efforts todevelop fluorinated GTPs with even shorter fluorocarbonchains are currently underway.■ ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acsapm.5c04519.Additional figures: IR spectra, NMR spectra, SEC traces,temperature-dependent XRD profiles, AFM images,Table 4. Summary of Advancing and Receding ContactAngles and Contact Angle Hysteresissample name θAa (°) θA‑maxb (°) θRc (°) Δθd (°)GTP−C6F13 128 ± 1 −e 78 ± 1 50GTP-EG2-co-C6F1375 120 ± 2 −e 65 ± 2 55GTP-EG2-co-C6F1360 119 ± 2 −e 53 ± 1 66GTP-EG2-co-C6F1350 119 ± 1 −e 45 ± 1 74GTP-EG2-co-C6F1325 (130 ± 3)f 160 ± 2 7 ± 1 (>123)fGTP−EG2 93 ± 4 −e (<5)g (>88)gaAdvancing contact angle of a water droplet. bMaximum advancingcontact angle in stick-and-slip process. cReceding contact angle of awater droplet. Values are presented as mean ± standard deviation (n= 5). dContact angle hysteresis (θA − θR).eNo stick-and-slip behaviorwas observed. fAppropriate advancing contact angle was notobtainable due to stick-and-slip behavior. The data was obtainedfrom the averaged value at the droplet volume from 5 to 10 μL.gAppropriate receding contact angle was not obtainable because thecontact angle was smaller than 5°.ACS Applied Polymer Materials pubs.acs.org/acsapm Articlehttps://doi.org/10.1021/acsapm.5c04519ACS Appl. Polym. Mater. 2026, 8, 3023−30323030https://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsapm.5c04519/suppl_file/ap5c04519_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsapm.5c04519?goto=supporting-infopubs.acs.org/acsapm?ref=pdfhttps://doi.org/10.1021/acsapm.5c04519?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asrheological measurements, and contact angle measure-ments (PDF)■ AUTHOR INFORMATIONCorresponding AuthorTaichi Ikeda − Research Center for Macromolecules andBiomaterials, National Institute for Materials Science,Tsukuba, Ibaraki 305-0044, Japan; Biomimetics Center,Tokyo University of Technology, Hachioji, Tokyo 192-0982,Japan; orcid.org/0000-0001-6650-5798;Email: IKEDA.Taichi@nims.go.jpAuthorMasafumi Yoshio − Research Center for Macromolecules andBiomaterials, National Institute for Materials Science,Tsukuba, Ibaraki 305-0044, Japan; Graduate School ofChemical Sciences and Engineering, Hokkaido University,Sapporo, Hokkaido 060-8628, Japan; Japan Science andTechnology Agency, Precursory Research for EmbryonicScience and Technology (PRESTO), Kawaguchi, Saitama332-0012, Japan; orcid.org/0000-0002-1442-4352Complete contact information is available at:https://pubs.acs.org/10.1021/acsapm.5c04519Author ContributionsT.I.: Conceptualization, synthesis, instrumental analysis,discussion, writing original draft, review and editing, andvisualization. M.Y.: Instrumental analysis (XRD), computa-tional modeling, polarized optical microscopy image, dis-cussion, review and revision of the draft.NotesThe authors declare no competing financial interest.■ ACKNOWLEDGMENTSThis work was financially supported by Grant-in-Aids forScientific Research C, 25K08756 (JSPS). M.Y. also acknowl-edges financial support from Japan Science and TechnologyAgency, PRESTO, JPMJPR23QB.■ REFERENCES(1) Chen, Y.; Luo, C.; Hu, F.; Huang, Z.; Yue, K. Recent Advancesin Fluorinated Polymers: Synthesis and Diverse Applications. Sci.China: Chem. 2023, 66, 3347−3359.(2) Jaye, J. A.; Sletten, E. M. Recent Advances in the Preparation ofSemifluorinated Polymers. Polym. Chem. 2021, 12, 6515−6526.(3) Hori, H.; Tanaka, H.; Tsuge, T.; Honma, R.; Banerjee, S.;Ameduri, B. Decomposition of Fluoroelastomer: Poly(vinylidenefluoride-ter-hexafluoropropylene-ter-tetrafluoroethylene) Terpolymerin Subcritical Water. Eur. Polym. 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