1. Introduction
It is well known that fluoroalkanoyl peroxide [R
F-C(=O)OO(O=)C-R
F: R
F = fluoroalkyl group] is a useful tool for the synthesis of two-fluoroalkyl end-capped oligomers [R
F-(M)
n-R
F: M = radical polymerizable monomers] [
1,
2,
3]. These fluoroalkyl end-capped oligomers are attractive polymeric materials because they can exhibit a variety of unique properties such as high solubility, surface active properties, and nanometer size-controlled self-assembled molecular aggregates through the aggregation of end-capped fluoroalkyl segments in oilgomers, which cannot be achieved by the corresponding non-fluorinated and randomly fluoroalkylated polymers [
4,
5]. In these fluoroalkyl end-capped oligomers, especially, fluoroalkyl end-capped oligomers containing various hydroxyl segments such as monool, triol, and tetraol can cause gelation in water and polar organic media such as methanol and ethanol, whose behavior is governed by the synergistic interactions of the aggregation of fluoroalkyl segments within oligomers and the intermolecular hydrogen bonding related to the hydroxyl segments [
6,
7,
8,
9]. In this way, the exploration of novel fluoroalkyl end-capped oligomers containing numerous hydroxyl segments is of particular interest, from the developmental viewpoints of new fluorinated functional materials. In a variety of hydroxylated polymers, much attention has been focused on the synthetic sugar-containing polymers (glycopolymers), which possess the pendent gluconic residues (pentaol units), owing to their role as biomimetic analogues and their applications in biomedical and technological fields such as paints and cosmetics [
10,
11,
12,
13,
14,
15,
16,
17,
18,
19]. In fact, poly(allylamine) can react with gluconolactone in water to provide the gluconamide-substituted polymers, successively affording the hydrogel through the interaction of the corresponding polymers with borax [
20]. Similarly, the
d-gluconamide unit-containing methacrylate monomer can be copolymerized with AIBN (2,2′-azobisisobutyronitrile) in the presence of methyl acrylate as comonomer to afford the corresponding glycopolymers [
21]. These glycopolymers also have high potential use as polymeric surfactants [
22]. Therefore, the studies on the preparation of novel gluconamide unit-containing polymers bearing longer fluoroalkyl groups are of particular interest, because these polymers would exhibit not only the unique characteristics related to the gluconamide units but also the surface active characteristics imparted by longer fluoroalky groups. However, such studies have been very limited so far. In our fluoroalkyl end-capped oligomers, especially, two fluoroalkyl end-capped vinyltrimethoxysilane oligomer [R
F-(CH
2-CHSi(OMe)
3)
n-R
F] can undergo the sol-gel reaction under alkaline conditions to afford the corresponding fluorinated oligomeric silica nanoparticles [R
F-(CH
2-CHSiO
3/2)
n-R
F] [
22]. These fluorinated oligomeric silica nanoparticles have been also applied to the surface modification of glass to supply the superhydrophobic characteristic (water contact angle value: 180 degrees) with the oleophobic property [
22]. From these findings, it is highly suggested that the composite reactions of our present fluorinated vinyltrimethoxysilane oligomer with the gluconamide derivatives should lead the obtained composites to the creation of the unique surface characteristics imparted by not only longer fluoroalkyl groups, but also the gluconamide units. Here we report that two fluoroalkyl end-capped vinyltrimethoxysilane oligomers [R
F-(CH
2–CHSi(OMe)
3)
n-R
F] can undergo the sol-gel reaction in the presence of
N-(3-triethoxysilylpropyl)gluconamide [Glu-Si(OEt)
3] under alkaline conditions to afford the corresponding fluorinated oligomeric silica nanocomposites containing gluconamide units [R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2]. The modified surfaces treated with these obtained nanocomposites can provide the unique wettability states such as the highly oleophobic/superhydrophobic, highly oleophobic/superhydrophilic, and superoleophilic/superhydrophobic characteristics. These results will be described in this article.
3. Results and Discussion
Sol-gel reaction of fluoroalkyl end-capped vinyltrimethoxysilane oligomer [R
F-(CH
2CHSi(OMe)
3)
n-R
F; R
F = CF(CF
3)OC
3F
7 (R
F-(VM)
n-R
F)] proceeded smoothly in the presence of
N-(3-triethoxysilylpropyl)gluconamide [Glu-Si(OEt)
3] under alkaline conditions to afford the corresponding fluorinated oligomeric silica/Glu-SiO
3/2 nanocomposites [R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2]. These results are shown in
Scheme 1 and
Table 1.
The expected fluorinated composites were obtained in 31–86% isolated yields, and the obtained composites revealed a good dispersibility and stability in traditional organic media such as methanol, tetrahydrofuran, and 1,2-dichloroethane. Especially the fluorinated composites (Runs: 1–5), which were prepared under the feed amounts of Glu-Si(OEt)3 from 10 to 170 mg, afforded no dispersibility toward water; however, the fluorinated composites (Runs: 6–8), which were prepared under a higher feed amount of Glu-Si(OEt)3 greater than 170 mg, were found to give a good dispersibility and stability toward water.
The size of the fluorinated composites in
Table 1 was measured in methanol by dynamic light-scattering (DLS) measurements at 25 °C, because these composites can reveal the good dispersibility in methanol.
Table 1 also shows that each size of the composites is nanometer size-controlled fine particles from 33 to 72 nm (number-average diameter).
FE-SEM photograph of the R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2 nanocomposites (Runs 4 and 7 in
Table 1) methanol solutions was recorded, and the results are shown in
Figure 1.
Electron micrograph also shows the formation of fluorinated nanocomposite fine cubic-type particles with a mean diameter of 56 and 45 nm, respectively, and the similar size values to those (37.4 ± 9.0 and 51.1 ± 6.5 nm) of DLS measurements were observed in FE-SEM measurements (see Runs 4 and 7 in
Table 1).
To verify the surface active characteristics of the nanocomposites in
Table 1, these fluorinated nanocomposites have been applied to the surface modification of glass, and we have measured the dodecane and water contact angle values on these modified surfaces. The results are shown in
Table 2.
As shown in
Table 2, water contact values are, in general, dependent upon the feed ratios of the R
F-(VM)
n-R
F oligomer and the Glu-Si(OEt)
3 employed, increasing with lower feeds amounts of Glu-Si(OEt)
3 in R
F-(VM)
n-R
F/Glu-(Si(OEt)
3 from 108 to 180 degrees (superhydrophobic surface). A similar result was observed in the dodecane contact angle values, increasing from 56 to 112 degrees except for Run 1, although the original fluoroalkyl end-capped vinyltrimethoxysilane oligomeric silica nanoparticles [R
F-(VM-SiO
3/2)
n-R
F] can give a usual oleophobic (dodecane contact angle value: 46 degrees) with a superhydrophobic property (water contact angle value: 180 degrees).
The water contact angle values on the modified glass surfaces treated with the fluorinated nanocomposites, which were prepared under the greater feed amounts of Glu-Si(OEt)
3 from 0.44 to 1.75 mmol, were found to decrease from 133–137 to 0 degrees (superhydrophilic surface) over 15 or 25 min except for Run 8, indicating that the hydrophobic fluoroalkyl segments are replaced by the hydrophilic gluconamide segments in the nanocomposites when the environment is changed from air to water. The relatively higher feed amounts (0.44–0.88 mmol) of Glu-Si(OEt)
3 in the nanocomposite preparation illustrated in
Scheme 1 would enable the smooth surface arrangement of the hydrophilic gluconamide segments to provide the completely superhydrophilic surface through the flip-flop motion between the fluoroalkyl groups and gluconamide segments in the nanocomposites. A similar flip-flop motion between longer fluoroalkyl groups and hydrophilic segments has been already reported to exhibit the hydrophilic characteristic with an oleophobic property on the modified surfaces [
24,
25,
26,
27,
28]. Therefore, the nanocomposites which were prepared under relatively lower feed amounts (0.03 mmol) of Glu-Si(OEt)
3, can supply a highly oleophobic/superhydrophobic characteristic (dodecane and water contact angle values: 112 and 180 degrees) on the modified surface, due to the lower content of hydrophilic gluconamide segments in the nanocomposites.
The fabrication of a superoleophobic surface is, in general, difficult due to the lower surface tension of oils than that of water. Thus, a highly oleophobic (superoleophobic) surface can be realized by lowering the surface energy and enhancing the surface roughness [
29,
30,
31,
32,
33]. Similarly, it is well known that a superhydrophobic surface can be created by the architecture of the roughness surface through the sol-gel reactions of the longer alkyl chain-containing silane coupling agents such as octadecyltrichlorosilane and hexadecyltriethoxysilane in the presence of silica nanoparticles and tetraethoxysilane under alkaline conditions [
34,
35]. Therefore, in order to clarify such unique surface wettability illustrated in
Table 2, we have studied the surface roughness of the modified glasses treated with the R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2 nanocomposites possessing the highly oleophobic/superhydrophobic characteristic (Run 2 in
Table 2: dodecane contact angle value: 112 degrees and water contact angle value: 180 degrees) by using FE-SEM (field emission scanning electron microscopy) measurements and DFM (dynamic force microscopy) measurements, respectively. We have also studied the surface roughness of the modified surfaces possessing a similar wettability (highly oleophobic/superhydrophobic characteristic) (Run 1 in
Table 2) and usual oleophobic and hydrophobic characteristics (Run 8 in
Table 2) including the original fluoroalkyl end-capped vinyltrimethoxysilane oligomeric silica nanoparticles [R
F-(VM-SiO
3/2)
n-R
F], for comparison. The results are shown in
Figure 2,
Figure 3,
Figure 4 and
Figure 5.
As shown in
Figure 2A, the architecture of the effective roughness was observed on the modified surface treated with the R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2 nanocomposites possessing a highly oleophobic/superhydrophobic property. Such roughness of surface was also observed in the nanocomposites possessing a similar wettability depicted in
Figure 3A. The topographical image of the modified glass surface treated with the nanocomposites possessing a highly oleophobic/superhydrophobic property (
Figure 2B) can afford a higher roughness characteristic (the roughness average value: Ra value = 166 nm), compared with that (Ra value = 129 nm) of the modified surface possessing a lower dodecane contact angle value: 74 degrees (see
Figure 3B). Such a higher Ra value should enable the modified surface to supply a highly oleophobic/superhydrophobic characteristic. Especially, the introduction of an air cushion into rough deposits of our present nanocomposite particles could create such a unique superoleophobic/superhydrophobic characteristic on the modified surface. In fact, it was reported that the introduction of a proper rough surface microstructure could make a flat hydrophobic surface more hydrophobic due to the introduction of an air cushion beneath the water droplet [
36]. On the other hand, the FE-SEM and DFM measurements (see
Figure 4 and
Figure 5) show that the modified surfaces treated with the R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2 nanocomposites possessing a usual oleophobic/hydrophobic property and the pristine R
F-(VM-SiO
3/2)
n-R
F oligomeric nanoparticles can provide relatively smooth roughness, because these Ra values are 9 and 7 nm, respectively, indicating that such relatively smooth surfaces should supply the usual oleophobic/hydrophobic or oleophobic/superhydrophobic characteristic to the modified surfaces.
We tried to achieve the surface modification of not only the glass but also the polyethylene terephthalate (PET) fabric swatch by using the R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2 nanocomposites (Run 2 in
Table 1) under similar conditions, and the dodecane and water contact angle values on the modified PET fabric swatch were measured. The modified PET fabric swatch can exhibit the similar dodecane and water contact angle values: 111 and 180 degrees to those of the modified glass surfaces depicted for Run 2 in
Table 2. Especially, FE-SEM pictures of the modified PET fabric swatch show that the fluorinated nanocomposite particles are not only filled up between the PET fibers, but are also uniformly coated on the PET fibers (
Figure 6B), compared with that of the pristine PET fabric (
Figure 6A). Here, we tried to apply this modified PET fabric swatch to the separation membrane for the separation of the mixture of the fluorocarbon oil (1
H-tridecafluorohexane) and the hydrocarbon oil (dodecane: blue-colored with Quinizarin Green SS), because the modified PET fabric swatch can provide a highly oleophobic/superhydrophobic characteristic on the modified surface, and the results are illustrated in
Figure 7.
As shown in
Figure 7C, the surface appearance of the modified PET fabric swatch was quite similar to that of the pristine PET fabric swatch
Figure 7B. In addition, it was demonstrated that the modified PET fabric swatch is effective for the separation of blue-colored hydrocarbon oil and fluorocarbon oil to isolate the transparent colorless fluorocarbon oil as shown in
Figure 7C; although the pristine PET fabric swatch was not able to separate the mixture under similar conditions (see
Figure 7B). This finding is due to the highly oleophobic/superhydrophobic characteristic of the modified PET fabric swatch.
As illustrated in
Scheme 1 and
Table 1, the expected fluorinated oligomeric silica nanocomposites containing gluconamide units are prepared through the sol-gel reactions under alkaline conditions. Especially, as mentioned before, the higher feed amounts of Glu-Si(OEt)
3 greater than 0.21 mmol can lead the obtained nanocomposites to a good dispersibility toward water. This finding suggests that the fluorinated nanocomposites can cause gelation toward water through the synergistic interaction between the aggregation of the end-capped fluoroalkyl groups and the intermolecular hydrogen bonding related to the hydroxyl segments in the gluconamide units in the nanocomposites by controlling the sol-gel conditions (for example; by changing the alkaline concentrations). In fact, we have succeeded in preparing the R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2 nanocomposites, which can cause gelation toward water, by changing the feed amounts of both 25 % aqueous ammonia and methanol from 1.0 to 0.6 and 5.0 to 15 mL, respectively (see
Table 3).
The gelling fluorinated nanocomposites (see
Figure 8) were applied to the surface modification of the PET fabric swatch under similar conditions to those of
Table 2, and we have measured the dodecane and water contact angle values on the modified PET fabric swatch. The results are shown in
Table 4.
As shown in
Table 4, the modified PET fabric swatches were found to give a highly oleophobic/superhydrophobic characteristic, because the dodecane and water contact angle values are 89–102 and 180 degrees, respectively, quite different from the corresponding modified glass surfaces possessing a highly oleophobic/hydrophobic characteristic (see Runs 4 and 5 in
Table 2). The surface appearance of the modified PET fabric swatch is almost the same as that of the pristine PET fabric swatch (see
Figure 9), and the adhesion ability of the PET fabric swatch is strong enough that even after rubbing the modified surface with a finger, we cannot detect any released nanocomposites powder (see
Figure 10B). In contrast, the adhesion ability of the modified PET fabric swatch treated with the pristine R
F-(VM-SiO
3/2)
n-R
F oligomeric nanoparticles is not enough, and the corresponding fluorinated oligomeric nanoparticles were easily released from the modified surface after rubbing the surface with a finger (see
Figure 10A). Such strong adhesion ability would be due to the uniform modification on the PET fiber surface by the R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2 nanocomposite gels. In fact, FE-SEM images of the modified PET fabric and the pristine PET fabric swatches show that the nanocomposite gels can be uniformly coated on the PET fibers (see
Figure 11A,B), quite different from the FE-SEM picture of the modified PET fabric treated with the R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2 nanocomposites possessing no gelling ability as in
Figure 6B.
Furthermore, we have measured the dodecane and water contact angle values on the modified PET fabric swatches treated with the nanocomposite gels (Runs 9 and 10 in
Table 4) after immersing the corresponding swatches in water at room temperature for 1 day, and the results are also shown in
Table 4.
Quite interestingly, we can observe the wettability change from the highly oleophobic to the superoleophilic characteristic, while keeping the superhydrophobic characteristic on the modified fabric swatches only after immersing into water, because the dodecane contact angle values extremely decreased from 89–102 to 0 degrees after immersing into water. We have measured the FE-SEM images of the modified PET fabric swatch after immersing into water, and the results are illustrated in
Figure 12B. The FE-SEM images show that the nanocomposite gels are uniformly coated on each PET fiber to enhance the roughness on the PET fibers, different from that before immersing into water (see
Figure 12A). Such enhanced roughness would afford the different wettability through the immersing process into water.
In order to clarify the presence of fluorinated nanocomposites in the modified PET fabric swatch even after immersing into water, we have measured the EDX (Energy Dispersive X-ray) spectra of the modified PET fabric swatch treated with the R
F-(VM-SiO
3/2)
n-R
F/Glu-SiO
3/2 nanocomposites (Runs 9 and 10 in
Table 4) before and after immersing into water, the results are shown in
Figure 13 and
Figure 14.
EDX measurements show that the atomic contents of carbon, oxygen, nitrogen, fluorine, and silicon of the modified PET fabric swatch before and after immersing into water are as follows (see
Table 5).
We observe similar atomic values even after immersing into water. In addition, it was verified that fluorine and silicon atoms related to the fluorinated nanocomposites are uniformly dispersed on the modified PET fabric swatch before and after immersing into water by EDX mapping images illustrated in
Figure 13 and
Figure 14.
In this way, it was demonstrated that our present RF-(VM-SiO3/2)n-RF/Glu-SiO3/2 nanocomposite gels can be strongly coated into the PET fabric fiber networks due to the gelling ability of the nanocomposites.