New perfluoropolyether urethane methacrylates as surface modifiers: Effect of molecular weight and end group structure

Bongiovanni, Roberta Maria; Meo, Antonella; Pollicino, Antonino; Priola, Aldo; Tonelli, Claudio

doi:10.1016/j.reactfunctpolym.2007.09.009

Cited by 54 publications

(62 citation statements)

References 29 publications

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“…These results suggest that the outermost surface structure changed after exposure to water. [37][38][39][40][41] The atomic composition at the surface of the spin cast films measured by XPS in both the dry and pseudo-hydrated states also supported this model ( Figure 6). From the XPS characterization, the surface atomic ratios for C 1s /O 1s /F 1s /N 1s in the poly(VCN-alt-FAVE8) copolymer under dry conditions were estimated at 0.46/0.06/ 0.45/0.04, which corresponds to the theoretical atomic composition of the copolymer (C/O/F/N ¼ 0.45/0.03/0.46/0.06).…”

Section: Contact Angle Measurementsmentioning

confidence: 82%

Structural analysis and surface wettability of a novel alternated vinylidene cyanide with fluorinated vinyl ether copolymer

Ishige

Yamaguchi

Shinohara

et al. 2013

Polym J

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The structure, thermal properties and surface wettability of a novel alternating poly(VCN-alt-FAVE8) copolymer based on vinylidene cyanide (VCN) and perfluorooctyl ethyl vinyl ether (FAVE8) were investigated via both temperature-variable wide-angle X-ray powder diffraction (WAXD) and thin-film WAXD using a small angle incidence synchrotron radiation source, differential scanning calorimetry and contact angle measurements, respectively. The results of the WAXD and thin-film WAXD indicated that the alternating copolymer possessed a smectic liquid-crystalline phase at ambient temperature with a couple of fluoroalkyl side chains forming a bilayer with a 3.24 nm spacing and that the fluoroalkyl side chains in a thin-film on a Si wafer align perpendicularly to the surface. The isotropization temperature of the alternating copolymer was 150 1C, which was higher than the 29.5 1C for the poly(FAVE8) homopolymer. The spin-coated poly(VCN-alt-FAVE8) copolymer thin-film yielded high static contact angles for both water and oil similar to those for poly(perfluorooctyl ethyl acrylate), which is known as a superhydrophobic polymer. Dynamic contact angle and X-ray photoelectron spectroscopy measurements in both the dry and hydrated states suggested that the polar cyano and ether groups are enriched at the surface in the wet state, and this reorganization of the surface polar groups caused a large hysteresis of the contact angle.

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Section: Contact Angle Measurementsmentioning

confidence: 82%

Structural analysis and surface wettability of a novel alternated vinylidene cyanide with fluorinated vinyl ether copolymer

Ishige

Yamaguchi

Shinohara

et al. 2013

Polym J

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“…1 H NMR (DMF-d 7 /CClF 2 CFCl 2 ) δ (ppm) (Figures 2 and S3−S5 in the Supporting Information): 0.86−1.5 ((CH 3 ) 3 CCH 2 CF 2 − or (CH 3 ) 3 CCF 2 CH 2 − or CH 3 CH 2 CF 2 −), 3.3 (CF 3 −CH 2 −CF 2 , regioselective addition of • CF 3 radical onto CH 2 of VDF); 3.0 (CH 2 −CF 2 of VDF, normal VDF−VDF addition); 2.4 (CF 2 −CH 2 −CH 2 −CF 2 reverse addition of VDF). 19 F NMR (C 6 D 6 capillary THF/CClF 2 CFCl 2 ) or (DMF-d 7 /CClF 2 CFCl 2 ) δ (ppm) (Figure 3 Macromolecules XXXX, XXX, XXX−XXX been studied. In the first one, the HFPO oligomer was then reacted with water to convert the terminal acyl fluoride into a carboxylic acid.…”

Section: Methodsmentioning

confidence: 99%

“…In either method, the perfluorovinylether was characterized by 19 F NMR and 13 C NMR spectroscopies. Three vinyl fluorine atoms, shown as doublets of doublets, are evident at −117, −124, and −138 ppm in the 19 F NMR spectra (Figures 1 and S1 in the Supporting Information) corresponding to the F a , F b , and F c in the vinyl group, respectively (oligo(HPFO)−OCF c CF a F b ). The 13 C NMR spectrum ( Figure S2) shows a triplet of doublets and a doublet of triplets centered at 148 and 130 ppm assigned to  CF 2 and −OCF groups, respectively.…”

Section: Methodsmentioning

confidence: 99%

“…For the same reason, viscosimetry was not used. However, it was of interest to use both 1 H and 19 F NMR spectra that are complementary. The 19 F NMR spectra display the presence of: (i) the characteristic signals assigned to VDF in normal head to tail addition VDF-VDF dyads and reversed head to head dyads at −92 ppm, −113, and −116 ppm, respectively; (ii) the expected signals assigned to oligo(HFPO) chain centered at −80 and −144 ppm, and the signal centered at −110, −120, and −127 ppm assigned to CF 2 of VDF and CF 2 and CF of macromonomer in the VDF-oligo(HFPO) dyad (Figures 3 and S6−S10).…”

Section: Methodsmentioning

confidence: 99%

“…These end-labels (CF 3 − or (CH 3 ) 3 C−) enabled the calculation of the molar amount of VDF in the polymer (including head-to-head or head-to-tail percentages). From the molar amount of VDF in the polymer and using 19 F NMR spectroscopy, the molar amount of trifluorovinyl oligo(HFPO) macromonomer could be determined along with molecular weight. The best labels were obtained from • CF 3 radicals, generated from a perfluorinated hyperbranched radical, capable of initiating the radical copolymerization of VDF with a macromonomer containing oligo(HFPO) units.…”

Section: Introductionmentioning

confidence: 99%

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Radical Copolymerization of Vinylidene Fluoride (VDF) with Oligo(hexafluoropropylene oxide) Perfluorovinyl Ether Macromonomer To Obtain PVDF-g-oligo(HFPO) Graft Copolymers

Friesen

Améduri

2015

Macromolecules

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The synthesis of PVDF-g-oligo(HFPO) graft copolymers, where VDF and HFPO stand for vinylidene fluoride and hexafluoropropylene oxide, respectively, is presented. First, an oligo(HFPO)− OCFCF 2 macromonomer was prepared from two methods starting from oligo(HFPO) acyl fluoride in 34 to 54% yield. Then, the radical copolymerization of VDF with that comonomer, initiated by tert-butyl peroxypivalate (TBPPi) or perfluoro-3-ethyl-2,4-dimethyl-3-pentyl persistent radical (PPFR) was studied under various conditions. The resulting PVDF-g-oligo(HFPO) graft copolymers were produced in good isolated yields (74 to 89%). The molar percentages and molecular weights of the graft copolymers were assessed by 19 F and 1 H NMR spectroscopy. Molar percentages of VDF and oligo(HFPO)−OCFCF 2 comonomers reached up to 99% and 11%, respectively, while the molecular weights ranged from 25 000 to 77 000 g/mol. Their thermal properties were also studied and showed: (1) satisfactory thermostability (T d ) in the 410 to 494°C range under air and (2) melting temperature (T m ) between 138 to 159°C, while (3) the glass transition (T g ) ranged from −79 to −54°C.

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Perfluoropolyether polymers by UV curing: design, synthesis and characterization

Bongiovanni

Medici

Zompatori

et al. 2011

Polymer International

Self Cite

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Perfluoropolyether (PFPE) structures can be functionalized with acrylic groups using appropriate hydrogenated acrylic monomers: the macromers obtained are highly reactive under UV irradiation, and fluorinated polymers can be obtained. In the first part of this work is described the synthesis of new PFPE (meth)acrylic oligomers by extending OH-terminated fluorinated chains with urethane groups and reactive acrylic functions. The photopolymerization reaction of each product is then reported followed by the characterisation of the main thermal, mechanical and surface properties of UV-cured coatings. The polymers have good thermal resistance and fair mechanical and chemical resistance. More interestingly they show very low refractive index and low surface tension. For these latter properties the products can be advantageously used in highly demanding applications such as photonic devices and nano-patterning.

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New perfluoropolyether urethane methacrylates as surface modifiers: Effect of molecular weight and end group structure

Cited by 54 publications

References 29 publications

Structural analysis and surface wettability of a novel alternated vinylidene cyanide with fluorinated vinyl ether copolymer

Structural analysis and surface wettability of a novel alternated vinylidene cyanide with fluorinated vinyl ether copolymer

Radical Copolymerization of Vinylidene Fluoride (VDF) with Oligo(hexafluoropropylene oxide) Perfluorovinyl Ether Macromonomer To Obtain PVDF-g-oligo(HFPO) Graft Copolymers

Perfluoropolyether polymers by UV curing: design, synthesis and characterization

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