The RF-(VM-SiO2)n-RF/Talc composites were prepared by the sol-gel reaction of the
corresponding oligomer in the presence of talc particles under alkaline conditions.
The RF-(VM-SiO2)n-RF/Talc/Orgs composites were also prepared under the similar sol-gel reactions in the presence of Orgs. The RF-(VM-SiO2)n-RF/Talc composites were applied to the surface modification of glass to provide the oleophobic-superhydrophobic characteristic on the modified surface. However, the encapsulations of Orgs into the RF-(VM-SiO2)n-RF/Talc composite cores enable the modified glass surfaces to give the controlled wettabilities such as superoleophilic-superhydrophobic, superoleophobic-superhydrophilic, and superamphiphobic characteristics by changing the structures of the encapsulated Orgs. In fact, the encapsulations of low molecular weight aromatic compounds such as HMB and BPA as guest molecules into the fluorinated talc nanocomposite cores can impart the superoleophilic-superhydrophobic surfaces. On the other hand, the encapsulation of THSP and RF-COOH as guest molecules into the nanocomposite cores can afford the superoleophobic-superhydrophilic surfaces. In the encapsulation of RF-COOH as a guest molecule, the fluorinated talc nanocomposites, of whose preparative feed conditions consist of the relatively lower feed ratio of RF-COOH, were found to provide the superamphiphobic property on the surface. The encapsulation of
micrometer-size controlled PSt particles into the fluorinated composite cores can also proceed smoothly to afford the corresponding composites - encapsulated PSt particles. These micrometer-size controlled composite particle powders were applied to the packing materials for the column chromatography to separate the W/O emulsion. Recently, there has been a serious problem in increasing environmental pollution, such as the flood of oil in the Gulf of Mexico in 2010.55) Therefore, not only the RF-(VM-SiO2)n-RF/Talc/Orgs composites but also the RF-(VM-SiO2)n-RF/Talc/PSt composites have high potential as a wide variety of applicable materials for oil/water separation.
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Conclusions
The results obtained from this study are summarized as follows.
1. Sol-gel reactions of fluoroalkyl end-capped vinyltrimethoxysilane oligomer in the
presence of low molecular weight aromatic compounds (ArH) such as 1,1′-bi(2-naphthol)
(BINOL) and 2-hydroxy-4-methoxy benzophenone (HMB) were found to proceed smoothly
under alkaline conditions at room temperature to give the corresponding fluorinated oligomeric
silica nanocomposites - encapsulated aromatic compounds (BINOL and HMB) [RF-(VM-SiO2)n-RF/ArH nanocomposites]. UV light irradiation (λmax: 254nm) toward
RF-(VM-SiO2)n-RF/ArH nanocomposites showed that photodegradation of encapsulated ArH
was not observed at all in the fluorinated nanocomposites cores, although the parent ArH can
exhibit an effective photodegradation behavior under similar conditions. Especially,
encapsulated ArH can exhibit no weight loss corresponding to the contents of the aromatic compounds in the fluorinated nanocomposites even after calcination at 800 °C. Therefore,
fluoroalkyl end-capped vinyltrimethoxysilane oligomer has high potential for not only the
thermal resistance but also the UV resistance fluorinated polymeric materials.
2. Sol-gel reactions of fluoroalkyl end-capped vinyltrimethoxysilane oligomer in the
presence of magnesium carbonate fine particles were found to proceed smoothly under alkaline
conditions at room temperature to give the corresponding fluorinated oligomeric silica
nanocomposites - encapsulated magnesium carbonate nanoparticles
[RF-(VM-SiO2)n-RF/MgCO3]. The obtained composites have good dispersibility in traditional
organic media, and these composites are nanoparticles without agglomeration or coagulation
before and even after calcination at 800 °C. Parent magnesium carbonate undergoes the decarboxylation at around 400 °C to afford magnesium oxide; however, the more smooth
pyrolysis of the RF-(VM-SiO2)n-RF/MgCO3 nanocomposites can be observed at around 300 °C
to cause the selective formation of not magnesium oxide but magnesium fluoride. The modified
glass surfaces treated with the RF-(VM-SiO2)n-RF/MgCO3 nanocomposites after calcination
from 200 to 460 °C were found to exhibit the same superhydrophobic (water contact angle
value: 180 degrees) characteristic with good oleophobicity as that of the corresponding
nanocomposites before calcination. The transparent colorless modified
poly(methyl methacrylate) (PMMA) film was prepared by the treatment of the
RF-(VM-SiO2)n-RF/MgCO3 nanocomposites to give the good oleophobicity imparted by
fluorine in the composites on the modified surface. RF-(VM-SiO2)n-RF/MgCO3 nanocomposites
after calcination at 200 ~ 800 °C were also applied to the surface modification of PMMA films, and refractive indices of the obtained transparent colorless PMMA films were found to decrease
with increasing the calcination temperatures of the nanocomposites, indicating that magnesium
fluoride is likely to form in the composites by increasing the calcination temperatures.
3. Fluoroalkyl end-capped vinyltrimethoxysilane oligomeric silica
nanocomposites - encapsulated magnesium oxide particles [RF-(CH2-CHSiO2)n-RF/MgO nanocomposites; n = 2, 3; RF = CF(CF3)OC3F7] were prepared by the sol-gel reactions of the
corresponding oligomer [RF-(CH2-CHSi(OMe)3)n-RF] in the presence of magnesium oxide
nanoparticles under alkaline or non-catalytic conditions, respectively. These sol-gel reactions
were found to afford the two kinds of morphology-controlled fluorinated nanocomposite
particles; that is, the alkaline conditions can supply the spherical fine nanoparticles, and the
non-catalytic conditions can afford the linearly arrayed fluorinated oligomeric nanocomposite particles. Interestingly, the linearly arrayed nanocomposites provide a poor water-resistance
ability toward their encapsulated magnesium oxide, leading the magnesium hydroxide through
the hydrolysis process; however, it was demonstrated that the spherical fine nanoparticles can
give a perfect water-resistance ability toward the magnesium oxide in their particle cores under
similar conditions. More interestingly, the spherical fluorinated nanocomposite particles - encapsulated magnesium oxide were applied to the surface modification of glass to
provide a highly oleophobic/superhydrophobic characteristic on the surface. In addition, the
spherical fluorinated nanocomposite particles - encapsulated magnesium oxide were applicable
to the surface modification of PMMA film to exhibit the oleophobic characteristic imparted by
fluoroalkyl segments in the composites on the modified surface. Magnesium oxide in the
nanocomposites can also have a similar surface orientational ability to that of the fluoroalkyl
segments in the composites. In contrast, the corresponding linearly arrayed fluorinated nanocomposite particles can give the uniformly dispersibility toward the PMMA film to supply
the oleophobic property imparted by longer fluoroalkyl segments in the composites on the
surface and even on the reverse side.
4. Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2-CHSi(OMe)3)n-RF; n = 2, 3; RF = CF(CF3)OC3F7 (RF-(VM)n-RF oligomer)] can undergo the sol-gel reaction in the presence of talc particles under alkaline conditions at room temperature to provide the
corresponding fluorinated oligomeric silica/talc nanocomposites (RF-(VM-SiO2)n-RF/Talc).
A variety of guest molecules such as 2-hydroxy-4-methoxybenzophenone (HMB), bisphenol
A (BPA), bisphenol AF, 3-(hydroxysilyl)-1-propanesulfonic acid (THSP), and
perfluoro-2-methyl-3-oxahexanoic acid (RF-COOH) are effectively encapsulated into the RF-(VM-SiO2)n-RF/Talc composite cores to afford the corresponding fluorinated
nanocomposites - encapsulated these guest molecules. The R -(VM-SiO ) -R /Talc
composites - encapsulated low molecular weight aromatic compounds such as HMB and BPA
can exhibit a superoleophilic-superhydrophobic characteristic on the surfaces; however, the
RF-(VM-SiO2)n-RF/Talc composites - encapsulated THSP and RF-COOH exhibit a
superoleophobic-superhydrophilic characteristic on the modified surfaces. In these
nanocomposites, the RF-(VM-SiO2)n-RF/Talc/THSP composites are applicable to the surface modification of polyester fabric, and the modified polyester fabric possessing a
superoleophobic-superhydrophilic characteristic on the surface can be used for the membrane
for oil (dodecane)/water separation. In addition, the RF-(VM-SiO2)n-RF/Talc
composites - encapsulated micrometer-size controlled cross-linked polystyrene particles can be
also prepared under similar conditions, and the obtained composite white-colored particle
powders are applied to the packing material for the column chromatography to separate water-in-oil (W/O) emulsion.
Publications
1) H. Sawada, Y. Oikawa, Y. Matsuki, and T. Saito, “UV Resistance of Encapsulated Low
Molecular Weight Aromatic Compounds in Fluoroalkyl End-Capped Trimethoxyvinylsilane
Oligomer/Silica Nanocomposites”, Polym. Adv. Technol., 25, 388 ~ 395 (2014).
2) Y. Oikawa, T. Saito, S. Idomukai, T. Tanaka, M. Nishida, and H. Sawada, “Preparation of
Magnesium Carbonate Nanoparticles Encapsulated by Nanocomposites Material Derived
from Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomer – Application to the Surface
Modification of Glass and Poly(methyl methacrylate)”, J. Fluorine Chem., 177, 70 ~ 79
(2015).
3) Y. Oikawa, Y. Goto, M. Nishida, and H. Sawada, “Preparation of Morphology-Controlled
Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric Silica/Magnesium Oxide
Nanocomposite Particles: Development of Magnesium Oxide Nanocomposite Particles
Possessing a Water-Resistance Ability”, J. Sol-Gel Sci. Technol., submitted.
4) Y. Oikawa, T. Saito, S. Yamada, M. Sugiya, and H. Sawada, “Preparation and Surface
Property of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomer/Talc
Composite-Encapsulated Organic Compounds:Application for the Separation of Oil and Water”, ACS
Appl. Mater. Interfaces, 7, 13782 ~ 13793 (2015).
(not described in this thesis)
5) J. Suzuki, Y. Takegahara, Y. Oikawa, M. Chiba, S. Yamada, M. Sugiya, and H. Sawada,
“Preparation of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric
Silica/Poly(tetrafluoroethylene) Nanocomposites Possessing a
Superoleophilic/Superhydrophobic Characteristic: Application to the Separation of Oil and
Water”, J. Sol-Gel Sci. Technol., 81, 611 ~ 622 (2017).
6) H. Sawada, Y. Suto, T. Saito, Y. Oikawa, K. Yamashita, S. Yamada, M. Sugiya, and J.
Suzuki, “Preparation of RF-(VM-SiO2)n-RF/AM-Cellu Nanocomposites, and Use Thereof for the Modification of Glass and Filter Paper Surfaces: Creation of a Glass
Thermoresponsive Switching Behavior and an Efficient Separation Paper Membrane”, Polymers, 2017, 9, 92; doi:10.3390/polym9030092.