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纸质出版日期:2008-9-20,
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于庆杰, 马学虎, 郝婷婷, 袁达忠. 含氟高分子/SiO2杂化疏水材料的制备及涂层表面性质[J]. 高分子学报, 2008,(9):874-879.
YU Qingjie, MA Xuehu, HAO Tingting, YUAN Dazhong. SYNTHESIS AND SURFACE PROPERTIES OF FLUORINATED ORGANICINORGANIC HYBRID COATINGS[J]. Acta Polymerica Sinica, 2008,(9):874-879.
于庆杰, 马学虎, 郝婷婷, 袁达忠. 含氟高分子/SiO2杂化疏水材料的制备及涂层表面性质[J]. 高分子学报, 2008,(9):874-879. DOI: 10.3724/SP.J.1105.2008.00874.
YU Qingjie, MA Xuehu, HAO Tingting, YUAN Dazhong. SYNTHESIS AND SURFACE PROPERTIES OF FLUORINATED ORGANICINORGANIC HYBRID COATINGS[J]. Acta Polymerica Sinica, 2008,(9):874-879. DOI: 10.3724/SP.J.1105.2008.00874.
采用自由基溶液聚合与溶胶凝胶法相结合的方法制备了含氟高分子/SiO2杂化疏水材料.通过甲基丙烯酸十二氟庚酯(FA)与乙烯基三乙氧基硅烷(VTES)共聚合成了含氟硅共聚物(PFAS),进一步通过原硅酸乙酯(TEOS)与PFAS共聚物溶液共水解缩聚制备了具有含氟侧基的碳碳主链高分子和硅氧网络的含氟高分子/SiO2杂化疏水材料.研究结果表明,SiO2组分含量提高可以显著增加杂化材料薄膜的涂敷厚度,改善其耐久性能,而对杂化材料疏水性能的影响不大.
Fluorinated organic-inorganic hybrid materials were prepared using fluorine-containing monomers
silicone-containing monomers and tetraethyl orthosilicate by free-radical random copolymerization and sol-gel process
and applied as functional coatings onto aluminium alloy substrates.The fluorine-containing monomer used was dodecafluoroheptyl methyl acrylate(FA)
and silicone-containing monomer used was vinyltriethoxy silane(VTES).Tetraethyl orthosilicate(TEOS) was added to prepolymerized FA-co-VTES (PFAS) solution to co-hydrolyze and co-condense with different addition values.The influence of inorganic component content (TEOS) on the physical properties of the coating films were characterized by FTIR
TGA
GPC
SEM
and XPS.The surface free energies of fluorinated organicinorganic hybrid materials prepared were estimated from the contact angle data measured by sessiledrop method. Transparent coating films with smooth surface and uniform thickness could be obtained by the dip coating technique.FTIR and XPS results indicated that
owing to the strong electronegativity of the fluorine atoms
hydrophobic perfluoroalkyl groups were preferentially enriched to the outermost layer at the coating filmair interface
and three layers probably existed in the coating film.The upper layer oriented toward the air was composed of mainly perfluoroalkyl groups originating from FA
the intermediate layer was composed of hydrocarbon backbone chain originating from vinyl polymerization
and the bottom layer was composed of mainly —O—Si—O— network originating from TEOS.The fluorinated organicinorganic hybrid materials prepared were very hydrophobic and exhibited excellent water repellency.It was demonstrated that the water repellency properties of PFAS/SiO2 hybrid materials was governed by hydrophobic perfluoroalkyl groups of the outermost layer.The contact angles of the coating films for water and methylene iodide were extremely high
at 120.9° and 93°
respectively
for TEOS/FA mole ratios at 1∶1
and their surface free energies were about 11.48 mJ/m2.An important role of tetraethyl orthosilicate (TEOS) was to increase the density of the reaction sites of the —OH groups with the surface area and the thickness of fluorinated organicinorganic hybrid coatings.It has been confirmed by FTIR and GPC results that the increase of TEOS amounts could enhance hydrolysis and condensation of alkoxide precursors to improve the adhesion between hybrid coating and aluminum substrates by the formation of Si—O—Al bonds.It was also testified that the increase of inorganic silica content had a significant effect on the improvement of thickness of the bottom SiO2 layer
while it had a slight influence on the surface wettability of the hybrid coatings.The useful properties of fluorinated organicinorganic hybrid coatings like better thermal stability and improved corrosion resistance
could be significantly enhanced by the improvement of thickness of the bottom SiO2 layer and bonding between SiO2 layer and aluminum substrates.Morphology analysis by SEM showed that the introduction of flexible organic phase could relax the stress and reduce the microcracks caused by the volume shrinkage of silicon network during heat treatment process.The thermal stability of fluorinated organicinorganic hybrid materials studied by using TGA technique could be improved with TEOS amounts.The burning temperature should be less than 290℃ because the perfluoroalkyl groups begin to decompose from this temperature.
含氟杂化材料无机含量疏水性
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